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1.
Prashant K. Jain 《Chemical science》2020,11(33):9022
A range of chemical reactions occurring on the surfaces of metal nanoparticles exhibit enhanced rates under plasmonic excitation. It is not straightforward to distinguish between photochemical and photothermal effect using Arrhenius fitting of the reaction rates alone.In the recently published article: “Thermal effects – an alternative mechanism for plasmon-assisted photocatalysis”, Dubi et al.1 argue that the results of multiple works on plasmon-excited-induced bond dissociation reactions can be explained by a purely photothermal enhancement of the reaction rates and that no non-thermal effects are required to explain the enhanced rates resulting from plasmonic excitation. Their argument rests on a reproduction of the reaction rate data by an Arrhenius expression with a light-intensity-dependent local temperature at the surface of the nanoparticles.Dubi et al.‘s straightforward analysis may have general appeal for explaining rate enhancements in bond dissociation reactions observed under plasmonic excitation of metal nanostructures without invoking hot electron contributions. But there is one caveat that deserves recognition when undertaking such an analysis. As shown below, under certain common scenarios, it is practically impossible to distinguish between a photochemical (non-thermal) effect of light excitation and a purely photothermal one using a phenomenological Arrhenius fitting of the data alone.As per the Arrhenius equation, the rate of a reaction depends on the set temperature Ts as:1where R0 is a constant for a given reaction and reaction conditions and Ea is the apparent activation energy barrier for the reaction. As an aside, one should note that unlike the Eyring equation, which is preferred for non-gas-phase reaction kinetics involving a vibrational reaction co-ordinate, the pre-exponential factor in the Arrhenius equation is assumed to have a negligible temperature dependence.A photochemical explanation of plasmon-enhanced catalysis is that the apparent activation energy Ea is lower under plasmonic excitation as compared to its value, Edarka, in the dark. Thus, as per eqn (1), at a fixed temperature Ts, R will be higher under light excitation. In fact, the measured apparent activation barrier has been found to be dependent on the light intensity I. For the sake of the following argument, let us assume that the decrease in Ea is linearly dependent on the light intensity:Ea = Edarka − BI2where B is a proportionality constant with units of eV cm2 W−1 when Ea is expressed in units of eV and I in units of W cm−2. Note that B is expected to be wavelength-dependent. Eqn (2) can be written alternatively as:Ea = Edarka(1 − bI)3where b is simply B/Edarka and has units of cm2 W−1. From eqn (1) and (3):4Using a Taylor''s expansion around I = 0 (dark condition),5For the light-intensity regime (I ≪ 1/b), the higher order terms can be neglected, so one gets from eqn (4) and (5):6Thus, if one simply uses an Arrhenius analysis of the reaction rate, the reaction appears to be carried out at a hypothetical temperature that is higher than the actual temperature Ts by an amount proportional to the light intensity I:Tdummy = Ts(1 + bI)7where this hypothetical temperature is referred to as Tdummy. Eqn (7) is equivalently expressed as:Tdummy = Ts + aI8where a = bTs is the photothermal conversion coefficient with units of K cm2 W−1. Eqn (8) is identical to the expression used by Dubi et al. in their argument in favor of a purely photothermal effect. In other words, it would appear as if plasmonic excitation led to an increase in the temperature, but led to no change in the apparent activation barrier. Effectively, in a phenomenological Arrhenius analysis, the photochemical (non-thermal) effect of plasmonic excitation on the reaction is simply masked as a temperature increase.Thus, as shown in Fig. 1, an Arrhenius analysis with a as an adjustable fit parameter may be futile for practically distinguishing the photochemical action of plasmonic excitation, (i.e., a rate enhancement caused by a decrease in the activation barrier) from a purely photothermal effect (i.e., a rate enhancement caused by an increase in the surface temperature). Under such a scenario, for distinguishing these effects, it is necessary to have precise knowledge and/or control over the temperature at the surface of the nanoparticles, as correctly argued by Dubi et al.,1 but also acknowledged by practitioners2–4 in the field. It is well appreciated that the localized inhomogeneous nature of photothermal heating results in a temperature gradient extending out from the surface of the nanoparticles to the bulk of the medium. These gradients are small in magnitude under conditions where the heat dissipation rate can keep up with the energy deposition rate. However, in systems where heat transfer rates are limiting, significant non-uniformities in temperature and thermal bottlenecks can arise. Such cases necessitate spatially precise temperature-probing localized to the nanoparticle surface.Open in a separate windowFig. 1The reaction rate under plasmonic excitation, R, relative to that in the dark, Rdark, is plotted as a function of light intensity for (i) the photochemical case (red dots), where the activation barrier is decreased by plasmonic excitation (eqn (1) and (2) with B = 0.1 eV cm2 W−1) while the temperature is kept fixed and (ii) the purely photothermal model (black line), where the temperature is increased by plasmonic excitation (eqn (1) and (8)) with a = 54 K cm2 W−1) but the activation barrier remains unchanged. In both cases, Edarka = 1.21 eV and Ts = 600 K. The two models yield trends that are practically indistinguishable. 相似文献
2.
Wen-Xin Lv Yin Li Yuan-Hong Cai Dong-Hang Tan Zhan Li Ji-Lin Li Qingjiang Li Honggen Wang 《Chemical science》2022,13(10):2981
β-Difluoroalkylborons, featuring functionally important CF2 moiety and synthetically valuable boron group, have great synthetic potential while remaining synthetically challenging. Herein we report a hypervalent iodine-mediated oxidative gem-difluorination strategy to realize the construction of gem-difluorinated alkylborons via an unusual 1,2-hydrogen migration event, in which the (N-methyliminodiacetyl) boronate (BMIDA) motif is responsible for the high regio- and chemoselectivity. The protocol provides facile access to a broad range of β-difluoroalkylborons under rather mild conditions. The value of these products was demonstrated by further transformations of the boryl group into other valuable functional groups, providing a wide range of difluorine-containing molecules.A hypervalent iodine-mediated gem-difluorination allows the facile synthesis of β-difluoroalkylborons. An unusual 1,2-hydrogen migration, triggered by boron substitution, is involved.Organofluorine compounds have been widely applied in medicinal chemistry and materials science.1a–d In particular, the gem-difluoro moiety featuring unique steric and electronic properties can act as a chemically inert isostere of a variety of polar functional groups.2a–c Therefore, the construction of gem-difluoro-containing compounds has received considerable attention in recent years. Efficient methods including deoxyfluorination of carbonyl compounds,3a,b photoredox difluorination,4 radical difluorination,5 and cross-coupling reactions with suitable CF2 carriers6a–f are well developed. Alternatively, iodoarene-mediated oxidative difluorination reactions provide valuable access to these motifs by using simple alkenes as starting materials.7a–i Previously, these reactions were generally associated with a 1,2-aryl or 1,2-alkyl migration (Scheme 1a).7a–f Recent developments also allowed the use of heteroatoms as migrating groups, thereby furnishing gem-difluoro compounds equipped with easily transformable functional groups (Scheme 1b). In this regard, Bi and coworkers reported an elegant 1,2-azide migrative gem-difluorination of α-vinyl azides, enabling the synthesis of a broad range of novel β-difluorinated alkyl azides.7g Jacobsen developed an iodoarene-catalyzed synthesis of gem-difluorinated aliphatic bromides featuring 1,2-bromo migration with high enantioselectivity.7h Almost at the same time, research work from our group demonstrated that not only bromo, but also chloro and iodo could serve as viable migrating groups.7iOpen in a separate windowScheme 1Hypervalent iodine-mediated β-difluoroalkylboron synthesis.We have been devoted to developing new methodologies for the assembly of boron-containing building blocks by using easily accessible and stable MIDA (N-methyliminodiacetyl) boronates8a–c as starting materials.9a–e Recently, we realized a hypervalent iodine-mediated oxidative difluorination of aryl-substituted alkenyl MIDA boronates.9d Depending on the substitution patterns, the reaction could lead to the synthesis of either α- or β-difluoroalkylborons via 1,2-aryl migration (Scheme 1c). Recently, with alkyl-substituted branched alkenyl MIDA boronates, Szabó and Himo observed an interesting bora-Wagner–Meerwein rearrangement, furnishing β-difluorinated alkylboronates with broader product diversity (Scheme 1d).10 While extending the scope of our previous work,9d we found that the use of linear alkyl-substituted alkenyl MIDA boronates also delivers β-difluoroalkylboron products. Intriguingly, instead of an alkyl- or boryl-migration, an unusual 1,2-hydrogen shift takes place. It should be noted that internal inactivated alkenes typically deliver the 1,2-difluorinated products, with no rearrangement taking place.11a–d Herein, we disclose our detailed study of our second generation of β-difluoroalkylborons synthesis (Scheme 1e). The starting linear 1,2-disubstituted alkyl-substituted alkenyl MIDA boronates, unlike the branched ones,10 could be readily prepared via a two-step sequence consisting of hydroborylation of the terminal alkyne and a subsequent ligand exchange with N-methyliminodiacetic acid. This intriguing 1,2-H shift was found to be closely related to the boron substitution, probably driven thermodynamically by the formation of the β-carbon cation stabilized by a σ(C–B) bond via hyperconjugation.12a–dTo start, we employed benzyl-substituted alkenyl MIDA boronate 1a as a model substrate (9d the use of F sources such as CsF, AgF and Et3N·HF in association with PhI(OAc)2 (PIDA) as the oxidant and DCM as the solvent led to no reaction (entries 1 to 3). The use of Py·HF (20 equiv) successfully provided β-difluorinated alkylboronate 2a, derived from an unusual 1,2-hydrogen migration, in 39% yield (entry 4). By simply increasing the loading of Py·HF to 40 equivalents, a higher conversion and thus an improved yield of 61% was obtained (entry 5). No further improvement was observed by using a large excess of Py·HF (100 equiv) (entry 6). Other hypervalent iodine oxidants such as PhIO or PIFA were also effective but resulted in reduced yields (entries 7 and 8). A brief survey of other solvents revealed that the original DCM was the optimal one (entries 9 and 10).Optimization of reaction conditions
Open in a separate windowWith the optimized reaction conditions in hand, we set out to investigate the scope and limitation of this gem-difluorination reaction. The reaction of a series of E-type 1,2-disubstituted alkenyl MIDA boronates were first examined. As shown in Scheme 2, the reaction of substrates with primary alkyl (1b, 1e–g), secondary alkyl (1c, 1d), or benzyl (1h–k) groups proceeded efficiently to give the corresponding gem-difluorinated alkylboronates in moderate to good yields. Halides (1i–k, 1m) and cyano (1l) were well tolerated in this reaction. Of note, cyclic alkene 1n is also a viable substrate, affording an interesting gem-difluorinated cyclohexane product (2n).Open in a separate windowScheme 2Scope of 1,2-H migratory gem-difluorinations. a 4 h. b PIFA was used.To define the scope further, the substrates with Z configuration were also employed under the standard reaction conditions (eqn (1) and (2)). The same type of products were isolated with comparable efficiency, suggesting that the reaction outcome is independent of the substrate configuration and substrates with Z configuration also have a profound aptitude of 1,2-hydrogen migration. Nevertheless, the reaction of t-butyl substituted alkenyl MIDA boronate (1p) delivered a normal 1,2-difluorinated alkylboron product (eqn (3)). The 1,2-hydrogen migration was completely suppressed probably due to unfavorable steric perturbation. With an additional alkyl substituent introduced, a 1,2-alkyl migrated product was formed as expected (eqn (4)).1The gem-difluorination protocol was amenable to gram-scale synthesis of 2a (Scheme 3, 8 mmol scale of 1a, 1.24 g, 50%). To assess the synthetic utility of the resulting β-difluorinated alkylborons, transformations of the C–B bond were carried out (Scheme 3). Ligand exchange of 2a furnished the corresponding pinacol boronic ester 4 without difficulty, which could be ligated with electron-rich aromatics to obtain 5 and 6 in moderate yields. On the other hand, 2a could be oxidized with high efficiency to alcohol 7 using H2O2/NaOH. The hydroxyl group of 7 could then be converted to bromide 8 or triflate 9. Both serve as useful electrophiles that can undergo intermolecular SN2 substitution with diverse nitrogen- (10, 13), oxygen- (14), phosphorus- (11) and sulfur-centered (12) nucleophiles.Open in a separate windowScheme 3Product derivatizations. PMB = p-methoxyphenyl.To gain insight into the reaction mechanism, preliminary mechanistic studies were conducted. The reaction employing deuterated alkenyl MIDA boronate [D]-1a efficiently afforded difluorinated product [D]-2a in 72% isolated yield, clearly demonstrating that 1,2-H migration occurred (Scheme 4a). However, when the MIDA boronate moiety was replaced with a methyl group (15), no difluorinated product (derived from 1,2-migration) was detected at all, suggesting an indispensable role of boron for promoting the 1,2-migration event (Scheme 4b). Also, with a Bpin congener of 1a, the reaction led to large decomposition of the starting material, with no desired product being formed (Scheme 4b).Open in a separate windowScheme 4Mechanistic studies and proposals.Based on the literature precedent and these experiments, a possible reaction mechanism is proposed in Scheme 4c. With linear alkenyl MIDA boronates, the initial coordination of the double bond to an iodium ion triggered a regioselective fluoroiodination to deliver intermediate B. The regioselectivity could arise from an electron-donating inductive effect from boron due to its low electronegativity, consistent with previous observations.13a,b Thereafter, a 1,2-hydrogen shift, rather than the typical direct fluoride substitution of the C–I bond, provides carbon cation C. The formation of a hyperconjugatively stabilized cation is believed to be the driving force for this event.12a–d The trapping of this cation finally forms the product.In conclusion, we demonstrated herein our second generation of β-difluoroalkylboron synthesis via oxidative difluorination of easily accessible linear 1,2-disubstituted alkenyl MIDA boronates. An unexpected 1,2-hydrogen migration was observed, which was found to be triggered by a MIDA boron substitution. Mild reaction conditions, moderate to good yields and excellent regioselectivity were achieved. The applications of these products allowed the facile preparation of a wide range of gem-difluorinated molecules by further transformations of the boryl group. 相似文献
Entry | F− (equiv) | Oxidant | Solvent | Yield (%) |
---|---|---|---|---|
1 | CsF (2.0) | PIDA | DCM | 0 |
2 | AgF (2.0) | PIDA | DCM | 0 |
3 | Et3N·HF (40.0) | PIDA | DCM | 0 |
4 | Py·HF (20.0) | PIDA | DCM | 39 |
5 | Py·HF (40.0) | PIDA | DCM | 61 |
6 | Py·HF (100.0) | PIDA | DCM | 55 |
7 | Py·HF (40.0) | PIFA | DCM | 52 |
8 | Py·HF (40.0) | PhIO | DCM | 26 |
9 | Py·HF (40.0) | PIDA | DCE | 49 |
10 | Py·HF (40.0) | PIDA | Toluene | 46 |
3.
Fei Yu Tingting Huo Quanhua Deng Guoan Wang Yuguo Xia Haiping Li Wanguo Hou 《Chemical science》2022,13(3):754
Expediting the oxygen evolution reaction (OER) is the key to achieving efficient photocatalytic overall water splitting. Herein, single-atom Co–OH modified polymeric carbon nitride (Co-PCN) was synthesized with single-atom loading increased by ∼37 times with the assistance of ball milling that formed ultrathin nanosheets. The single-atom Co-N4OH structure was confirmed experimentally and theoretically and was verified to enhance optical absorption and charge separation and work as the active site for the OER. Co-PCN exhibits the highest OER rate of 37.3 μmol h−1 under visible light irradiation, ∼28-fold higher than that of common PCN/CoOx, with the highest apparent quantum yields reaching 4.69, 2.06, and 0.46% at 400, 420, and 500 nm, respectively, and is among the best OER photocatalysts reported so far. This work provides an effective way to synthesize efficient OER photocatalysts.Single-atom CoII-OH modified polymeric carbon nitride synthesized with increased single-atom loading under the assistance of ball milling exhibits high photocatalytic water oxidation activity with Co-N4OH as the highly active site.Massive fuel energy consumption induced environmental and ecological problems, especially the greenhouse effect, and the resultant extreme climates and rise in sea level are threatening human life.1 As a potential substitution for fuel energy, hydrogen energy conversion from solar energy via photocatalytic water splitting attracts great attention from scientists.2–5 However, the photocatalytic hydrogen evolution efficiency from overall water splitting is still restricted by the sluggish oxygen evolution reaction (OER) that involves energy absorption, four-electron transfer, breakage of O–H bonds, and formation of O–O bonds,6,7 and thus efficient OER photocatalysts become the key to achieving efficient overall water splitting. Though numerous hydrogen evolution photocatalysts have been reported, research on OER photocatalysts is mainly around a few semiconductors including BiVO4, WO3, Ag3PO4, α-Fe2O3, etc.8–11 and their activity is not high enough yet for practical applications. Therefore, exploring high-efficiency OER photocatalysts is still necessary.Polymeric carbon nitride (PCN) was first reported in 2009 (ref. 12) as a photocatalyst with a layered melon-type orthorhombic structure,13 and thereafter quickly became a “star” photocatalyst thanks to its advantages of being visible-light responsive and metal-free, non-toxic, and low cost, and its relatively high chemical stability.14 Because of several self-deficiencies including fast photogenerated charge recombination and a narrow optical absorption spectrum, PCN exhibits relatively low photocatalytic activity.15 Then, a series of strategies were put forward successively to enhance the photoactivity of PCN, such as enhancement of crystallinity,16 morphological control,17 structural modification18 (including extensively researched single atom modification in recent years19,20), exfoliation,21 construction of hetero-(homo-)junctions,22 and loading of noble metals.23 Though photocatalytic water splitting on PCN was extensively researched in the past, the research was mainly around the hydrogen evolution half-reaction used for exploring properties and the catalytic mechanism of photocatalysts, and little research was focused on the industrially useable overall water splitting process owing to the sluggish OER.15 Therefore, enhancing the photocatalytic OER activity of PCN becomes the key to practical applications.To increase OER rates of PCN, several kinds of methods were proposed, such as rational design of compound cocatalysts (e.g., CoOx, IrO2, CoP, CoPi, RhOx, RuOx, PtOx, MnOx, Co(OH)2, Ni(OH)2, and CoAl2O4 (ref. 24–30)), modification of carbon dots and carbon rings,31,32 fabrication of special architectures of PCN (e.g., PCN quantum dot stacked nanowires33), and single-atom (e.g., B, Co, and Mn34–36) modification. For instance, Zhao and coauthors prepared B and N-vacancy comodified PCN that exhibits the highest OER rate of ∼28 μmol h−1 (ref. 36) and recently their group further used these B doped PCN ultrathin nanosheets to fabricate a Z-scheme heterojunction for overall water splitting with a solar-to-hydrogen efficiency reaching ∼1.2%.37 Comparatively, PCN loaded with compound cocatalysts can only enhance OER activity to a limited degree and there are finite methods for carbon modification and special architecture fabrication. Single-atom modification shows a bright prospect, on account of metal atoms capable of being inserted into the framework of PCN and effectively increasing the OER activity. However, reported single metal atom modification routes are all based on direct ion adsorption on PCN or calcination of mixtures of metal salts and PCN feedstocks.34,35,38 New routes need be explored to increase effective loading of single atoms in PCN. Besides, the metal-OH structure is considered efficient for the OER,30,39,40 and a single metal atom-OH structure has never been reported for modification of PCN, though Mn–OH was thought to play a key role in the OER process.34Ball milling is an extensively used versatile and scalable way for preparation of heterogeneous catalysts and even single-atom catalysts,41,42 but was rarely used in synthesis of PCN-based single-atom photocatalysts. In this work, we synthesized single-atom Co–OH modified PCN (Co-PCN) with the single-atom content in PCN highly increased with the assistance of ball milling. The simple synthetic route is shown in Fig. 1a. PCN was ball-milled to obtain BM-PCN that then adsorbed Co2+ till saturation to form BM-PCN/Co which was calcined to obtain BM-PCN/Co-c (Co-PCN). For comparison, PCN was directly used to adsorb Co2+ till saturation to form PCN/Co which was calcined to obtain PCN/Co-c. PCN mainly comprises large blocks with the size of several micrometers (Fig. S1†), while BM-PCN contains massive irregular particles with the size reduced to several hundreds of nanometers (Fig. S2†), indicative of high efficacy of ball milling. BM-PCN/Co-c exhibits a similar morphology as BM-PCN (Fig. 1b and S3†) and PCN/Co-c exhibits a similar morphology to PCN (Fig. S4†), but the surface area and mesopore volume of BM-PCN and BM-PCN/Co-c are not higher than those of PCN and PCN/Co-c (Fig. S5†), manifesting that ball-milling and subsequent calcination did not form massive mesopores, which accords well with the particle size variation from several micrometers (before ball milling) to several hundreds of nanometers (after ball milling). However, the Co content in BM-PCN/Co-c, BM-PCN/Co, PCN/Co-c, and PCN/Co was measured to be 0.75, 0.50, 0.02, and ∼0.02 wt%, respectively, by inductively coupled plasma mass spectrometry (ICP-MS). The ∼37 times higher Co content in BM-PCN/Co-c than in PCN/Co-c suggests the ball-milling enhanced adsorption of Co2+ on surfaces of BM-PCN, which should arise mainly from the ball-milling induced increase of surface energy and adsorption sites.43Open in a separate windowFig. 1(a) Schematic illustration for synthesis of single-atom CoII-OH modified PCN (BM-PCN/Co-c); and (b) SEM, (inset in b) TEM, (c) AFM, (d) EDS elemental mapping, and (e) HAADF-STEM images of BM-PCN/Co-c.The TEM image shows the existence of small and ultrathin nanosheets in BM-PCN/Co-c (inset in Fig. 1b) which can also be observed in the atomic force microscopy (AFM) image with a thickness of ∼7–10 nm and lateral size of <70 nm (Fig. 1c), and formation of these ultrathin nanosheets results from the ball milling of PCN.44 It should be noted that most formed ultrathin nanosheets with high surface energy may stack into compact particles upon ball milling, leading to no increase of the total surface area. Energy dispersive X-ray spectroscopy (EDS) elemental mapping images of BM-PCN/Co-c indicate homogeneous distribution of C, N, O, and Co elements in the sample (Fig. 1d). The high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image of BM-PCN/Co-c shows massive white spots (marked by circles) with a mean size of <1 Å dispersed in the sample (Fig. 1e and S6†), which should correspond to single-atom Co.To further verify the single-atom Co structure in BM-PCN/Co-c, Co K-edge X-ray absorption near-edge structure spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) analysis were performed. As shown in Fig. 2a, the absorption-edge position of BM-PCN/Co-c is quite close to that of CoO and their peak positions are similar and far from those of other reference samples, indicating that the valence of Co in BM-PCN/Co-c is about +2. The bonding structure around Co was determined by Fourier transformed (FT) k3-weighted EXAFS analysis. As shown in Fig. 2b, a distinct single Co-ligand peak at ∼1.6 Å for BM-PCN/Co-c is observed, which prominently differs from the Co–Co coordination peak at ∼2.2 Å for Co foil and the CoII–O coordination peak at ∼1.7 Å for CoO. The wavelet transform (WT) contour plot of BM-PCN/Co-c shows only one intensity maximum (Fig. S7†), and the Cl 2p core-level XPS spectrum of BM-PCN/Co-c reveals no residue of Cl (Fig. S8†). These further indicate the single-atom dispersion of Co species. Apparently, the Co-ligand peak is almost consistent with the CoII–N peak for Co porphyrin, suggesting that the single-atom Co in BM-PCN/Co-c mainly coordinates with N. Least-square EXAFS curve fitting was performed to confirm quantitative structural parameters of CoII in BM-PCN/Co-c, as shown in Fig. 2c, S9, and S10 and Table S1.† Simple Co–N single-shell fitting of BM-PCN/Co-c (Fig. S10†) gave a coordination number of 5.6 ± 0.4 (Table S1†), that is, CoII coordinates with five atoms. Considering that the PCN monolayer provides four appropriate N coordination sites at most,45 CoII likely coordinates with four N atoms and one OH atom. Thus, we further performed Co–N4/Co–O double-shell fitting (Fig. 2c) and the obtained R-factor (0.0011) remarkably reduces relative to that from Co–N single-shell fitting (0.0035), indicative of rationality of the proposed CoII–N4OH structure. Confirmed Co–N and Co–O bond lengths are 2.04 and 2.15 Å, respectively (Table S1†).Open in a separate windowFig. 2(a) Co K-edge XANES and (b) EXAFS spectra of Co foil, Co porphyrin (Copr), CoO, Co3O4, Co2O3, and BM-PCN/Co-c; EXAFS (c) R space-fitting and (inset in c) K space-fitting curves of BM-PCN/Co-c; (d) optimized structure of PCN and Co-doped PCN with different doping configurations and calculated formation energies (e) of Co doped PCN; and (e) Co 2p and (f) O 1s core-level XPS spectra of samples.To further confirm rationality of the Co–N4OH coordination structure, density functional theory (DFT) calculations were conducted. As shown in Fig. 2d, three possible CoII coordination structures in the PCN monolayer were explored. The Co–N4OH structure without removal of H from PCN exhibits a much lower formation energy (∼0.15 eV) than Co–N4 and Co–N3 structures with removal of two H atoms from PCN (∼2.51 and 3.55 eV), demonstrating a high probability of existence of the Co–N4OH structure in BM-PCN/Co-c. This structure can also be evidenced by X-ray photoelectron spectroscopy (XPS). As shown in Fig. 2e, the Co 2p core-level XPS spectrum of BM-PCN/Co-c shows two distinct peaks at binding energies of 796.8 and 781.4 eV beside satellite peaks, corresponding to Co 2p1/2 and 2p3/2 of CoII ions.46 The spectrum of BM-PCN/Co also shows two Co 2p peaks but at a binding energy ∼1.1 eV higher, suggesting variation of the Co coordination structure from BM-PCN/Co to BM-PCN/Co-c. PCN/Co-c exhibits no peaks because of its low Co content. Fig. 2f shows O 1s core-level spectra of PCN, BM-PCN, BM-PCN/Co-c, and PCN/Co-c. All the samples exhibit one peak at a binding energy of ∼532.0 eV, ascribed to surface hydroxyl species,47 but an additional peak could be obtained for BM-PCN or BM-PCN/Co-c after deconvolution. The peak at a binding energy of ∼531.3 eV for BM-PCN should be assigned to adsorbed H2O at new active adsorption sites generated by ball milling. This peak can also be observed in the spectrum of BM-PCN/Co, but with a ∼0.1 eV shift to a higher binding energy (Fig. S11†) owing to the influence of adsorbed CoII ions. The peak at ∼531.2 eV for BM-PCN/Co-c should be assigned to Co–OH,48 given that there is only one O 1s peak for BM-PCN-c (synthesized by direct calcination of BM-PCN) (Fig. S11†). The calculated Co/O(–Co) molar ratio, based on the XPS data, is ∼1.07 (Table S2†), close to 1, consistent with the Co–N4OH coordination structure.In C 1s and N 1s core-level XPS spectra, BM-PCN, BM-PCN/Co-c, PCN/Co-c, and BM-PCN/Co exhibit similar peaks to PCN (Fig. S12a–d†), indicative of their similar framework structure which can also be evidenced by their similar N/C molar ratios, 1.53 (Table S3†), but the N–H peak of BM-PCN shifts ∼0.2 eV to a lower binding energy relative to that of PCN, likely arising from the ball-milling induced destruction of intralayer hydrogen bonds (Fig. S13†). The Co content in BM-PCN/Co, BM-PCN/Co-c, and PCN/Co-c is too low to cause detectable variation of C 1s and N 1s peaks. Similar FT-IR absorption bands of the samples (Fig. S14a and b†) also indicate their basic frame structure, but in enlarged spectra (Fig. S14c†), ν(C–N) and ν(C N) absorption bands of BM-PCN shift 16 cm−1 to a higher wavenumber and 19 cm−1 to a lower wavenumber, respectively, relative to those of PCN at 1242 and 1640 cm−1,49 likely resulting from the ball-milling induced hydrogen bond destruction, and the shift of these two absorption bands turns smaller for BM-PCN/Co-c, suggesting calcination-induced reforming of the destroyed hydrogen bonds, which is consistent with the XPS results (Fig. S12c†). Besides, BM-PCN exhibits a wider and relatively stronger ν(N–H)/ν(O–H) absorption band than PCN (Fig. S14a†), probably owing to the hydrogen bond destruction and new adsorbed H2O, while this absorption band for BM-PCN/Co-c becomes much weaker, suggesting hydrogen bond reforming and loss of new adsorbed H2O (Fig. 2f). Zeta potentials of the samples dispersed in water reflect variation of surface adsorbed hydroxyl species. As shown in Fig. S15a,† all the samples exhibit negative zeta potentials because of dissociation of surface hydroxyl species. The zeta potentials, following the order PCN (−24 mV) > BM-PCN (−41 mV) < BM-PCN/Co-c (−30 mV) ≈ PCN/Co-c (−28 mV), suggest the ball milling-induced increase of surface hydroxyls in BM-PCN and calcination-induced decrease in BM-PCN/Co-c, consistent with the FT-IR results.Solid-state 13C magic-angle-spinning nuclear magnetic resonance (NMR) spectra of PCN, BM-PCN, BM-PCN/Co-c, and PCN/Co-c show two similar peaks at chemical shifts of ∼164 and 156 ppm (Fig. S15b†), ascribed to C−NHx and N C–N, respectively,50 indicating their similar molecular framework, but in enlarged spectra, BM-PCN exhibits ∼0.3° movement of the N C–N peak to a lower chemical shift compared with PCN, because of the ball-milling induced hydrogen bond destruction, and the C−NHx peak of BM-PCN/Co-c moves ∼0.2° to a lower chemical shift, likely owing to formation of the C–N–Co structure whose peak lies close to the C−NHx peak.51 The XRD patterns of the samples are shown in Fig. S15c.† PCN and PCN/Co-c exhibit typical diffraction peaks of melon-type carbon nitride with a layered orthorhombic structure and peaks at 13.1° and 27.6° correspond to (210) and (002) facets, respectively,13,52 but BM-PCN reveals remarkably decreased peak intensity and ∼0.2° shift of the (002) peak to a lower 2θ (indicative of the increased interlayer distance) relative to PCN, demonstrating the ball-milling induced hydrogen bond destruction and substantial decrease of crystallinity. The remarkable decrease of crystallinity and almost no change of the surface area of BM-PCN, compared with those of PCN, further suggest that ball milling may form massive thin nanosheets (Fig. 1c) most of which stack into compact particles (Fig. 1b) owing to their high surface energy. In comparison with BM-PCN, BM-PCN/Co-c exhibits a narrower (002) peak, suggesting enhanced crystallinity owing to the calcination-induced hydrogen bond reforming, consistent with the FT-IR results. On the whole, it is likely the ball-milling induced destruction of hydrogen bonds that contributes largely to the increase of surface energy and new active adsorption centers and thus Co2+ adsorption on BM-PCN.Optical absorption capability of samples was investigated by UV-vis diffuse reflectance spectroscopy (DRS). As shown in Fig. 3a, BM-PCN/Co-c, BM-PCN, and PCN/Co-c exhibit considerably higher, lower, and similar optical absorption than/to PCN, respectively. For BM-PCN/Co-c, the optical absorption enhancement at a wavelength of <400 nm may benefit from the electron-rich Co that enhances π–π* transitions in heptazine rings,53 and the Urbach tail absorption should arise from the Co–OH doping.54,55 Bandgaps (Eg) of PCN, BM-PCN, BM-PCN/Co-c, and PCN/Co-c were roughly confirmed as 2.70, 2.81, 2.56, and 2.73 eV, respectively, via the formula Eg/eV = 1240/(λed/nm)56 where λed is the absorption edge determined by solid lines in the spectra. The wider Eg of BM-PCN probably results from the quantum size effect of massive ultrathin crystal nanosheets (Fig. 1c) formed by ball milling, and the narrower Eg of BM-PCN/Co-c arises from the Co–OH doping that was then verified by DFT calculations. As shown in Fig. S16,† the calculated Eg of BM-PCN/Co-c, ∼1.90 eV, is much smaller than that of PCN (2.57 eV), in accordance with the experimental results. For PCN, the conduction band (CB) is contributed by C 2p and N 2p orbitals and the valence band (VB) mainly by N 2p orbitals, while for BM-PCN/Co-c, the CB is contributed by Co 3d, C 2p, and N 2p orbitals and the VB mainly by Co 3d and N 2p orbitals (Fig. S16c and d†), effectively manifesting that the narrowing of Eg of BM-PCN/Co-c results from the Co–OH doping. In addition, there are prominent doping levels (Ed) in the bandgap of BM-PCN/Co-c, mainly contributed by Co 3d and O 2p orbitals (Fig. S16d†), effectively proving the Co–OH doping effect in BM-PCN/Co-c. Similar calculation results have been reported for Pt–OH modified carbon nitride.57 Given that the experimental Co content (0.75 wt%) is much lower than the theoretical (6.71 wt%), practical doping levels in the bandgap may approach more to the VB. CB edges of the samples (ECB) could be roughly determined by using Mott-Schottky plots (Fig. S17†) and their Fermi levels (Ef) were subsequently confirmed based on VB-XPS spectra (Fig. S18†). Energy band levels of the samples are shown in Fig. 3b, and it seems that ball milling causes a slight downshift of the VB edge (EVB) of BM-PCN, favorable for photocatalytic water splitting, but the Co–OH doping causes a slight downshift of ECB and upshift of EVB of BM-PCN/Co-c. It is noteworthy that the Ed close to the VB edge (EVB) can capture photogenerated holes58 and thus the single-atom Co–OH works as the active site for the OER (Fig. 3b).Open in a separate windowFig. 3(a) UV-vis diffuse reflectance spectra of PCN, BM-PCN, BM-PCN/Co-c, and PCN/Co-c; (b) energy band levels of the samples and schematic illustration for water oxidation on BM-PCN/Co-c; (c) photoluminescence spectra, (d) time-resolved fluorescence spectra, and (e) anodic photocurrent (Ja) response of the samples; and (f) EPR spectra of the samples in the dark and under visible light irradiation. Data in (d) are the results of fitting decay curves to a tri-exponential model. Dark Ja in (e) was set as zero for distinct comparison.Spectroscopy and photoelectrochemical tests were conducted to evaluate photogenerated charge separation and transfer performance. As shown in Fig. 3c, photoluminescence (PL) spectra of all the samples show one emission peak, basically corresponding to their bandgap emission. BM-PCN exhibits weaker PL intensity than PCN, revealing a decreased photogenerated charge recombination efficiency, which originates from faster charge transfer from the inside to the surface of ultrathin nanosheets (Fig. S19†) and trapped by surface states.59 BM-PCN/Co-c exhibits the lowest PL intensity and the PL intensity of PCN/Co-c is lower than that of PCN, which arises from the Ed capturing photogenerated holes to reduce their direct recombination with electrons beside the ultrathin nanosheet effect in BM-PCN/Co-c. Fig. 3d shows time-resolved fluorescence spectra of the samples. Decay curves were well fitted to a tri-exponential model (S3) and the obtained results are shown in Fig. 3d. Three lifetimes (τ1–τ3) and their mean lifetime (τm, 89.2 ns) of BM-PCN are all much longer than those of PCN (τm = 17.9 ns), further suggesting the faster charge transfer from the inside to the surface of ultrathin nanosheets in BM-PCN, decreasing the direct charge recombination efficiency, but with subsequent surface radiative recombination.60 Interestingly, the τ1–τ3 and τm (10.8 ns) of BM-PCN/Co-c are much shorter than those of PCN, which should result from faster transfer of holes to Ed that effectively decreases the charge recombination efficiency, with subsequent nonradiative energy transformation.61 The Co–OH doping effect also makes PCN/Co-c exhibit shorter τ1–τ3 and τm (16.5 ns) than PCN. Fig. 3e shows the photocurrent response of the samples. Their anodic photocurrent density follows the order PCN < PCN/Co-c < BM-PCN < BM-PCN/Co-c, indicating gradually increased photogenerated charge separation efficiencies,62 basically consistent with the PL results. The relatively high photocurrent response of BM-PCN benefits from the applied bias that effectively inhibits surface recombination of photogenerated charge carriers.To assess charge mobility of the samples, their electrochemical impedance spectroscopy (EIS) spectra were tested with high-frequency data simply fitted to an equivalent circuit (Fig. S20†). The obtained charge transfer resistance (Rct) follows the order PCN (26 Ω) > BM-PCN (18 Ω) ≈ PCN/Co-c (19 Ω) > BM-PCN/Co-c (13 Ω). Apparently, BM-PCN/Co-c exhibits smaller Rct than BM-PCN and PCN/Co-c, and PCN/Co-c exhibits smaller Rct than PCN, indicating the highest charge transfer performance of BM-PCN/Co-c63 which originates from the single-atom Co modification64 that may increase the electron density to facilitate charge transport. The smaller Rct of BM-PCN than that of PCN indicates the additional favorable effect of ultrathin nanosheets.65Fig. 3f shows electron paramagnetic resonance (EPR) spectra of the samples. All reveal one single Lorentzian line centered at a g of 2.0039, attributed to unpaired electrons in heptazine rings.66 In the dark, the EPR signal intensity follows the order PCN < BM-PCN < PCN/Co-c < BM-PCN/Co-c, and the stronger signal of BM-PCN than that of PCN results from formation of ultrathin nanosheets that enhances delocalization of unpaired electrons, while the stronger signal of BM-PCN/Co-c and PCN/Co-c mainly benefits from the Co doping that increases the delocalized electron density.67 Under visible light irradiation, the samples exhibit remarkable signal enhancement, following the sequence PCN < BM-PCN < PCN/Co-c < BM-PCN/Co-c, similar to that of the signal intensity in the dark, suggesting that the increase in the delocalized electron density facilitates charge photoexcitation. The high delocalized electron density favors charge transport, consistent with the EIS results, and the high photoexcited charge density benefits enhancement of photocatalytic activity.Photocatalytic OER activity of various samples was well evaluated using Ag+ as the sacrificial agent (Fig. S21†). The Co content in BM-PCN/Co-c was optimized according to the photocatalytic OER rates and BM-PCN-c exhibits no detectable OER activity (Fig. S22†), indicating indispensability of the Co–OH structure for the OER. The influence of the calcination temperature (Tc °C) of BM-PCN/Co on OER rates of BM-PCN/Co-c (Tc = 460) and BM-PCN/Co-cTc was investigated and BM-PCN/Co-c exhibits the highest photoactivity (Fig. 4a), manifesting that the optimal calcination temperature is 460 °C. Under both simulated solar light and visible light irradiation (λ ≥ 420 nm), BM-PCN/Co-c exhibits substantially higher OER activity than PCN/Co-c (Fig. 4b), further suggesting the significance of the single-atom Co loading amount, and remarkably higher activity than common PCN/CoOx (with 0.75 wt% Co, obtained via photodeposition) and BM-PCN-c/Co(OH)2 (with 0.75 wt% Co), demonstrating the high efficacy of the single-atom distribution of Co–OH in BM-PCN/Co-c. Besides, urea was used as the feedstock to synthesize carbon nitride (marked as PCN-urea) with a larger surface area (76 m2 g−1 (ref. 68)) than PCN, and PCN-urea was further used to synthesize PCN-urea/Co-c similar to the synthesis of BM-PCN/Co-c. The OER activity of BM-PCN/Co-c is prominently higher than that of PCN-urea/Co-c (with the optimized Co content and Co single atom distribution, Fig. S23†), suggesting the significant role of ball milling in fabricating the single-atom Co–N4OH structure. To quantitively compare photoactivity of the samples, their mean OER rates under visible light illumination for 2 h are shown in Fig. 4c. The OER rate of BM-PCN/Co-c can reach ∼37.3 μmol h−1, about 13.8, 28.7, 2.6, and 2.0 times those of PCN/Co-c, PCN/CoOx, BM-PCN-c/Co(OH)2, and PCN-urea/Co-c, respectively. Comparatively, less N2 was generated for BM-PCN/Co-c (Fig. S24†), further demonstrating the significance of single-atom Co–OH modification.Open in a separate windowFig. 4(a) The influence of the calcination temperature (Tc °C) of BM-PCN/Co on photocatalytic OER activity of BM-PCN/Co-c (Tc = 460) and BM-PCN/Co-cTc, under Xe-lamp illumination, with AgNo3 as the sacrificial agent; (b) photocatalytic oxygen evolution on various samples under Xe-lamp illumination with or without using a 420-nm filter; (c) corresponding OER rates of the samples in 2 h; (d) photocatalytic OER rates of BM-PCN/Co-c under irradiation with various monochromatic light sources for 12 h; (e) apparent quantum yields (AQYs) of BM-PCN/Co-c at different wavelengths and reaction times and the highest AQY at every wavelength, along with the UV-DRS spectrum; and (f) proposed mechanism for photocatalytic water oxidation on the single-atom CoII-OH structure.Photocatalytic oxygen evolution on BM-PCN/Co-c was also tested under monochromatic light irradiation (Fig. S25†). Apparently, BM-PCN/Co-c can exhibit OER activity even at a wavelength of 500 nm. The mean OER rate in 12 h decreases from 1.85 to 0.54 μmol h−1 with increasing wavelengths from 400 to 500 nm (Fig. 4d), independent of light intensity of the Xe lamp and is mainly dependent on optical absorption capability of BM-PCN/Co-c at various wavelengths (Fig. 3a). Fig. 4e shows apparent quantum yields (AQYs) of BM-PCN/Co-c at different reaction times and wavelengths. Basically, there are maxima of AQYs with increasing reaction time at every wavelength, suggesting the adverse effect of excessive photodeposited Ag on surfaces of samples. These maxima are shown in Fig. 4e and accord well with the UV-vis DRS spectrum with increasing wavelengths. The maxima of AQYs at 400, 420, 450, and 500 nm can reach 4.69, 2.06, 1.07, and 0.46%, respectively. Compared with the reported photocatalytic OER results for PCN (Table S4†), BM-PCN/Co-c exhibits the top-class performance.To investigate chemical stability of BM-PCN/Co-c, the cyclic OER experiment was conducted. After five consecutive runs, OER rates of BM-PCN/Co-c decrease less (Fig. S26a†), with the morphology similar to the original (Fig. S26b†). Co single atoms in the sample could still be distinctly observed by HAADF-STEM (Fig. S26c and d†). In addition, N 1s core-level XPS spectra of BM-PCN/Co-c are almost similar before and after the cyclic experiment (Fig. S26e†). These indicate the high stability of the basic framework structure of the sample. However, Co 2p core-level spectra show remarkable differences before and after the experiment, not only the CoII peak shift, probably owing to ion (e.g., IO4−) adsorption, but also formation of a large amount of CoIII (Fig. S26f†). Coexistence of CoII/CoIII may suggest the photocatalytic OER mechanism.The proposed OER mechanism based on the Co–OH structure is shown in Fig. 4f, according to the reported results in Mn doped PCN.34 Four holes are needed to complete four oxidation steps and obtain one O2 molecule. The first step starting with one hole may involve formation of the CoIII O bond. The Co–N4OH structure should facilitate the water oxidation more compared with that of Co–N4 without OH coordination, by leaving out the initial adsorption process of H2O molecules.34 On the whole, the high photocatalytic OER activity of Co-PCN benefits from the Co–N4OH structure that not only effectively enhances optical absorption, and charge separation and transport, but also works as the highly active site for the OER. 相似文献
4.
Herein, we report for the first time single Au38 nanocluster reaction events of highly efficient electrochemiluminescence (ECL) with tri-n-propylamine radicals as a reductive co-reactant at the surface of an ultramicroelectrode (UME). The statistical analyses of individual reactions confirm stochastic single ones influenced by the applied potential.Herein, we report for the first time single Au38 nanocluster reaction events of highly efficient electrochemiluminescence (ECL) with tri-n-propylamine radicals as a reductive co-reactant at the surface of a Pt ultramicroelectrode (UME).Single entity measurements have been introduced by Bard and Wightman based on the collisions/reactions of individual nanoparticles and molecules at an ultramicroelectrode (UME).1–9 Since then, the field of single entity electrochemistry has gradually attracted several research groups and has become a frontier field of nanoelectrochemistry and electroanalytical chemistry.8,10–14 For instance, it has been shown that the chemistry of the electrode surface plays an important role in the collision/reaction events and the kinetics of reaction processes.15–21 Dasari et al. reported that hydrazine oxidation and proton reduction can be detected using single Pt nanoparticles on the surface of a mercury or bismuth modified Pt UME, and the material of the electrode was found to affect the shape of current–time transients.22,23 Fast scan cyclic voltammetry provides better chemical information about transient electrode–nanoparticle interactions, which is otherwise difficult to obtain with constant-potential techniques.24 There are only a few reports on photoelectrochemical systems including semiconductor nanoparticles designed to detect single nanoparticles in the course of photocatalysis processes.25–28 More importantly, owing to the nature of stochastic processes of single entity reactions, statistical analyses have shown substantial influences on the understanding of the underlying processes.Electrochemiluminescence or electrogenerated chemiluminescence (ECL),29 as a background-free technique,30–32 was also utilized to detect individual chemical reactions and single Pt nanoparticle collisions based on the reaction between the Ru(bpy)32+ complex and tri-n-propylamine (TPrA) radicals on the surface of an ITO electrode.2,33,34 It was found that the size of the nanoparticles, the origin of the interaction between particles and the electrode surface, the concentration of species generation, and the lifetime of individual electrogenerated nanocluster species (i.e., Au382+, Au383+, and Au384+) in conjunction with the reactivity of those oxidized species with co-reactant radical intermediates (i.e., TPrA radical) play crucial roles in the frequency of the ECL reaction events leading to individual ECL responses. More strikingly, a higher ECL reaction frequency is directly proportional to the amount of collected ECL light.21 Chen and co-workers also employed ECL to study stationary single gold-platinum nanoparticle reactivity on the surface of an ITO electrode.35 Lin and co-workers monitored the hydrogen evolution reaction in the course of “ON” and “OFF” ECL signals.36 Recently, we performed a systematic and mechanistic ECL study of a series of gold nanoclusters, with the general formula of Aun(SC2H4Ph)mz (n = 25, 38, 144, m = 18, 24, 60 and z = −1, 0, +1), where near-infrared (NIR) ECL emission was observed.37 There are several enhancement factors, such as catalytic loops38,39 that improve the signal to noise ratio. The Wightman group was able to report single ECL reactions based on the capability of ECL.7 Furthermore, thus far, we have explored ECL mechanisms and reported the ECL efficiency of five different gold nanoclusters i.e., Au25(SR)181−, Au25(SR)180, Au25(SR)181+, Au38(SR)240 and Au144(SR)600, among which the Au38(SR)240/TPrA system revealed outstanding ECL efficiency, ca. 3.5 times higher than that of Ru(bpy)32+/TPrA as a gold standard. Therefore, we decided to focus on the Au38 (SR)240/TPrA system. It was discovered that the ECL emission of these nanomaterials can be tuned through varying the applied potential and local concentration of the desired co-reactant.Herein, for the first time we report on ECL via a single Au38(SC2H4Ph)24 nanocluster (hereafter denoted as Au38 NC) reaction (eq. (1)) in the vicinity of an UME in the presence of TPrA radicals as a reductive co-reactant.1where x is the oxidation number that can be either 0, 1, 2, 3 or 4. Single ECL spikes (Fig. 1A) along with ECL spectroscopy were used for elucidating individual reaction events. Indeed, each single ECL spike demonstrates a single Au38(x−1)* reaction product. Au38 NCs were synthesized according to procedures reported by us and others, and fully characterized using UV-Visible-NIR, photoluminescence, 1HNMR spectroscopy and MALDI mass spectrometry to confirm the Au38 nanocluster synthesis (details are provided in ESI, Sections 1–3, Fig. S1–S4†).38,40,41Fig. 2 (left) shows a differential pulse voltammogram (DPV) in an anodic scan of a 2 mm Pt disc electrode immersed in 0.1 mM Au38 acetonitrile/benzene solution containing 0.1 M TBAPF6 as the supporting electrolyte. There are five discrete electrochemical peaks at which Au380 was oxidized to Au38+ (E°′ = 0.39 V), Au382+ (E°′ = 0.60 V), and Au383+/4+ (E°′ = 0.99 V) and reduced to Au38− (E°′ = −0.76 V) and Au382− (E°′ = −1.01 V).38,40,41Open in a separate windowFig. 1(A) An example of the reaction event transient of 10 μM Au38 in benzene/acetonitrile (1 : 1) containing 0.1 M TBAPF6 in the presence of 20 mM TPrA at 0.9 V vs. SCE, acquired at 15 ms time intervals using a 10 μm Pt UME. The white dashed-line indicates the threshold to identify single ECL spikes. (B) Illustration of a single nanocluster ECL spike. (C) ECL instrumentation with an inset showing ECL spike generation in the vicinity of the Pt UME.Open in a separate windowFig. 2Anodic DPV for Au38 (left), reaction energy diagram of Au382+ and TPrA· (middle) along with the ECL–voltage curve (right) in an anodic potential scan at a 2 mm Pt disk electrode immersed in a solution of 10 μM Au38 with 20 mM TPrA.The rich electrochemistry of Au38 NCs is well-matched with that of co-reactants such as TPrA to generate near infrared-ECL (NIR-ECL), and the ECL emission efficiency of the Au38/TPrA system is 3.5 times larger than that of the Ru(bpy)32+/TPrA co-reactant ECL system.27Thus, it is of utmost interest to investigate the ECL generation of the above co-reactant system in single reactions, which improves the ECL signal detection sensitivity. To perform the ECL experiment a solution of 10 μM Au38 NC with 20 mM TPrA was prepared. We first confirmed the ECL light generation of such solution along with its blank solution containing only TPrA using a typical 2 mm diameter Pt disk electrode (Fig. 2, S5 and S6†).A 10 μm Pt UME electrode, which is electrochemically inert (Fig. S7†), was utilized to investigate the ECL of single NC reactions under potentiostatic conditions, at which a specific positive bias potential was applied to oxidize both Au38 and TPrA. Fig. 1A shows a typical ECL–time transient current curve (ECL intensity versus time) at 0.90 V vs. SCE, which was acquired using a photomultiplier tube (PMT, R928) for a duration of 1800 s at data acquisition time intervals of 15 ms (Fig. 1C and ESI, Section 3†). Fig. 1B represents an exemplary event of a single ECL spike with a sharp increase followed by a decay in the ECL intensity. It is observed from the many spikes in Fig. 1B that this process can reoccur with a high probability in the vicinity of the UME, probably due to an electrocatalytic reaction loop (Fig. 1C). Indeed, ECL intensity was enhanced in this way as an already relaxed species, i.e., Au38z+1*, participates in an oxidation step to regenerate Au38z+1 to react with the TPrA radical (TPrA˙).Once photons resulting from the excited state relaxation in the vicinity of the UME are captured by the PMT, individual reaction events can be observed (Fig. 1A with the instrumentation schematic shown in Fig. 1C). As shown in Fig. 3A, there are many ECL spikes during 1800 s of measurement, each of which represents an individual ECL generation reaction in the vicinity of the UME surface. It is worth noting that there are several spikes with various intensities. This is most likely due to the Brownian motion which is random movement due to the diffusion of individual nanocluster species such as Au380, Au381+, Au382+, etc., electrogenerated at the local applied potentials. Long and co-workers42 proposed that silver nanoparticle collision on the surface of a gold electrode follows Brownian motion, leading to several types of surface-nanoparticle response peak shapes. In fact, the observed ECL spikes, shown in Fig. 1C, with a rise and an exponential decay suggested that Au38 nanocluster species diffuse directly through the electrode double-layer, move towards the tunneling region of the electrode surface, collide42 and become oxidized, react with TPrA radicals thereafter to produce excited states, and emit ECL. It is worth emphasizing that this path could be partially different for each individual nanocluster owing to the angle and direction relative to the electrode surface. The single Au38 NC reaction behaviour at various bias potentials was investigated following the electrochemical energy diagram shown in Fig. 2, middle. For example, at a bias potential of 0.70 V (the green spot on the DPV in Fig. 2), Au380 undergoes two successive oxidation reactions to Au382+ and TPrA oxidation and deprotonation start to generate TPrA·. In fact, at a very close oxidation potential to Au382+, TPrA is also oxidized to its corresponding cation radical (ca. 0.80 V vs. SCE) Fig. S6,† followed by deprotonation to form the TPrA radical.38 The TPrA· with a very high reduction power (E°′ = −1.7 eV)43 injects one electron to the LUMO orbital of the nanocluster and forms excited state Au38+*, as illustrated in the reaction energy diagram in Fig. 2, middle.38 Then, Au38+* emits ECL light while relaxing to the ground state. For another instance, at 1.10 V vs. SCE (the red spot on the DPV in Fig. 2), Au380 is oxidized to Au383/4+ feasibly. At this potential, the TPrA radical is generated massively in the vicinity of the electrode. The efficient electron transfer between the TPrA radical and Au383/4+ generates both Au382+* and Au383+* that emit light at the same wavelength of 930 nm.38 The results of such interactions produced a transient composed of many ECL events (Fig. 3A), which is an indication of bias potential enforcement on the nanocluster light emission.Open in a separate windowFig. 3Single-nanocluster ECL photoelectron spectroscopy of Au38. ECL–time transients (A), statistics of the number of photons (B), histogram of the single reaction time between sequential spikes (C) and accumulated ECL spectrum (D) for a 10 μm Pt UME at 1.1 V immersed in a 10 μM Au38 nanocluster solution in benzene/acetonitrile (1 : 1) containing 0.1 M TBAPF6 in the presence of 20 mM TPrA. (E)–(H) The counterpart plots to (A)–(D) for the UME biased at 0.7 V. # represents the number.We further tried to collect the current–time traces of such events; however, owing to the high background current originating from the high concentration of TPrA relative to that of the nanocluster, no noticeable spikes in the current were observed.In order to study the photochemistry and understand deeply the single nanocluster reactions, ECL–time transients were collected at different applied potentials (i.e., 0.7, 0.8, 0.9 and 1.1 V vs. SCE) as labelled in green, brown, purple, and red on the DPV in Fig. 2, respectively. The transients were further analysed using our home-written MATLAB algorithm adapted from that for nanopore electrochemistry.44 The population of individual events was identified by applying an appropriate threshold to discriminate ECL spikes from the noise as demonstrated in Fig. 1A. In fact, the applied algorithm also assisted us to learn about the raising time and intensity of each spike, as well as photons of individual spikes. For instance, Fig. 3A shows another typical transit for 1800 s at an UME potential bias of 1.1 V for the ECL events. Indeed, the integrated area of each peak, the charge of the photoelectrons at the PMT, is directly proportional to the number of photons emitted from individual reactions (see ESI, Section 5†). Basically, the PMT amplifies the collected single photon emitted in the course of light-to-photoelectron conversion (see ESI, Section 6 and Fig. S8†) and translates a single photon into photoelectrons. The extracted charge of each ECL reaction, QECL, was then converted to the corresponding number of photons by dividing by the gain factor, g, which is 1.55 × 106 (Fig. S8†), following eqn (2):2The histograms of the number of photons show a Gaussian distribution (Fig. 3B) with a reaction frequency of 53.5 ± 2.9 at E = 1.1 V, whereas at a lower potential of 0.7 V the reaction frequency drops to 18.5 ± 1.7 (Fig. 3F). This indicates that there is a three-fold lower reaction occurrence at the lower potential. The integration of the Gaussian fitting at 1.1 V and 0.7 V also reveals a three-fold drop from 3.3 × 105 to 1.2 × 105 photons over 1800 s.To further explore the effect of electrode potential bias on the single Au38 NCs ECL reaction, potentials lower than 1.1 and higher than 0.7 V, ca. 0.8 and 0.9 V (brown and purple labels in Fig. 2), were applied. In fact, the resulting ECL–time transients show a lower population of single spikes (Fig. S12A and ESI,†). The integrated Gaussian curve values support the ECL–time transient observations with ∼4.1 × 104 and ∼6.5 × 104 photons, respectively. In fact, it is unlikely that the PMT would get more than two events in the duration, owing to the following reasons: (i) it has been shown that only 5.5% of incoming photons can be effectively converted to photoelectron signals by our R928 PMT during our absolute efficiency calibration, ESI Section 6 and Fig. S8–S19†;45 (ii) spherical ECL emission is proven to be detected for a substantial small part upon examination of our detection system for the absolute ECL quantum efficiency;45 (iii) Au38 nanocluster ECL emissions occur at 930 nm, which is almost at the wavelength detection limit of our PMT response curve.38,45In addition, we evaluated the stochastic (a series of random events at various probability distributions) nature of the observed events and extracted the reaction time interval (τ) at various potentials. The resulting graph shows an exponential decay (Fig. 3C) as expressed in eqn (3):3where frequency (λ) gives the mean rate of the event and A represents the fitting amplitude. One can expect to obtain the distribution of the number of emitted photons and spatial brightness function. In fact, the exponential decay is a clear indication of random single reaction events as Whiteman and co-workers described for a 9,10-diphenylanthracene (DPA) ECL system in the annihilation pathway.7,46 At a potential of 1.1 V, λ and A are found to be 4.98 ± 0.02 ms−1 and 80.4 ± 3.2, whereas at 0.7 V, λ and A turned out to be 32.9 ± 1.6 ms−1 and 9.5 ± 0.1 (Fig. 3C and G). Indeed, the lower potential of 0.70 V vs. SCE is high enough to generate the TPrA radical along with Au382+, thereby leading to excited Au38+*, Fig. 3E. One can conclude that at the applied potentials of 0.7 V and 1.1 V, Au380 is oxidized to Au382+ and Au384+, resulting in the generation of Au38+* and Au383+* under static conditions. Thus, there are higher populations of ECL spikes with no discrepancy in the number of collected photon distributions. However, at two intermediate potentials, i.e., 0.8 and 0.9 V, a dynamic behaviour which is due to the mixed oxidation of Au38 species, in the vicinity of the UME, is observed. In fact, at these two applied potentials, the local concentration of the corresponding gold nanoclusters (i.e., Au383+ and Au384+) is not sufficient to produce significant ECL spikes. We also attempted to collect the ECL spectrum using a charge-coupled device (CCD) camera, which is relatively more sensitive in the NIR region (e.g., λ > 900 nm, Fig. S16†). Fig. 3D and H display an accumulated spectrum at 1.1 and 0.7 V vs. SCE, which is collected for 30 minutes. The fitted accumulated ECL spectrum indicates an ECL peak emission at 930 nm and supports higher reactivity at 1.1 V than that at 0.7 V.38 To confirm that the observed ECL spikes and accumulated spectra are generated based on the oxidation of Au38 nanoclusters in the presence of TPrA radicals, ECL–time transients were recorded upon holding an applied potential at which no faradaic process occurs. Fig. S11† represents ECL–time curves and accumulated ECL spectra at 0.0 V and 0.4 V. One can notice that no appreciable ECL signal can be observed.In addition, we investigate the Pearson cross-correlation (ρ) between the intensities of ECL spikes with τ as shown in Fig. S14† in which there is a positive correlation at 0.7 and 1.0 V and a negative correlation at 0.8 and 0.9 V. In fact, ρ evaluates whether there is a stationary random process between the two defined parameters (see ESI, Section 6†). Interestingly, the frequency of the reaction at different applied potentials revealed decay from 0.7 to 0.8 V, followed by an upward trend to 0.9 and 1.1 V vs. SCE (Fig. S15†). This could be additional support for the transition stage at 0.8 and 0.9 V, where the applied potential as the major driving force to generate oxidized forms (e.g., Au383+ and Au384+) governs the flux of the nanocluster species that reach the vicinity of the electrode. Furthermore, the effectiveness of electron transfer reaction kinetics between the radical species, i.e., Au38z+1 and TPrA radical, competes with the flow of the incoming nanoclusters. It is worth mentioning that each of the ECL single event experiments was repeated three times, and very similar results were obtained. Moreover, lower (5 μM) and higher (20 μM) concentrations of Au38 in the presence of 20 mM were tested. In fact, the former shows a smaller number of single reactions; however the later revealed a larger number of multiple reactions (Fig. S13†).In summary, in this communication we demonstrated that Au38 NC ECL at the single reaction level can be monitored using a simple photoelectrochemical setup following a straightforward protocol. Indeed, we have rich basic knowledge about the ECL mechanisms of various gold nanoclusters with different charge states (Au25(SR)181+, Au25(SR)180, Au25(SR)181−) and various sizes (Au25(SR)180, Au38(SR)240, Au144(SR)600) in fine detail. Thus, the ECL emission mechanisms of gold clusters, including the contribution of each charge state and influence of various concentrations of co-reactants, are well known. For instance, in our previous studies38,39,47–49 we clearly identified three charge states of an Au25(SR)181−/TPrA system and we discovered that at a high concentration of TPrA the reduction in the bulk solution of gold nanoclusters influences the ECL emission wavelength. We also have learnt that the Au38/TPrA system is a co-reactant independent of co-reactant concentration. Furthermore, an extensively higher concentration of TPrA provides a dominant reaction over any unknown decomposition reaction at higher oxidation states of Au38. It was discovered that the population of ECL reactions is directly governed by the applied bias potential on a Pt UME. This work is a strong indication of the high sensitivity of the ECL technique in detecting single ECL reactions in a simple solution, which complements those reported by the Bard group using rubrene, for instance, embedded in an organic emulsion in the presence of TPrA or oxalate as a co-reactant.50,51 These systems needed a substantial ECL enhancement in the presence of an ionic liquid as the supporting electrolyte and emulsifier. The current approach can be further extended to investigate other molecules and nanomaterials'' electrocatalytic processes at the single reaction level. 相似文献
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Hlne Beucher Johannes Schrgenhumer Estíbaliz Merino Cristina Nevado 《Chemical science》2021,12(45):15084
A chelation-assisted oxidative addition of gold(i) into the C–C bond of biphenylene is reported here. The presence of a coordinating group (pyridine, phosphine) in the biphenylene unit enabled the use of readily available gold(i) halide precursors providing a new, straightforward entry towards cyclometalated (N^C^C)- and (P^C)-gold(iii) complexes. Our study, combining spectroscopic and crystallographic data with DFT calculations, showcases the importance of neighboring, weakly coordinating groups towards the successful activation of strained C–C bonds by gold.Pyridine and phosphine directing groups promote the C–C activation of biphenylene by readily available gold(i) halides rendering a new entry to (N^C^C)- and (P^C)-gold(iii) species.Activation of C–C bonds by transition metals is challenging given their inertness and ubiquitous presence alongside competing C–H bonds.1 Both the intrinsic steric hindrance as well as the highly directional character of the p orbitals involved in the σC–C bond impose a high kinetic barrier for this type of processes.2,3 Biphenylene, a stable antiaromatic system featuring two benzene rings connected via a four-membered cycle, has found widespread application in the study of C–C bond activation. Since the seminal report from Eisch et al. on the oxidative addition of a nickel(0) complex into the C–C bond of biphenylene,4 several other late transition metals have been successfully applied in this context.5 Interestingly, despite the general reluctance of gold(i) to undergo oxidative addition,6 its oxidative insertion into the C–C bond of biphenylene was demonstrated in two consecutive reports by the groups of Toste7a and Bourissou,7b respectively. The high energy barrier associated with the oxidation of gold could be overcome by the utilization of gold(i) precursors bearing ligands that exhibit either a strongly electron-donating character (e.g. IPr = [1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene])7a or small bite angles (e.g. DPCb = diphosphino-carborane).7b,8 In line with these two approaches, more sophisticated bidentate (N^C)- and (P^N)-ligated gold(i) complexes have also been shown to aid the activation of biphenylene at ambient temperature (Scheme 1a).7c,dOpen in a separate windowScheme 1(a) Previous reports on oxidative addition of ligated gold(i) precursors onto biphenylene. (b) This work: pyridine- and phosphine-directed C–C bond activation of biphenylene by commercially available gold(i) halides.In this context, we hypothesized that the oxidative insertion of gold(i) into the C–C bond of biphenylene could be facilitated by the presence of a neighboring chelating group.9 This approach would not only circumvent the need for gold(i) precursors featuring strong σ-donor or highly tailored bidentate ligands but also offer a de novo entry towards interesting, less explored ligand templates. However, recent work by Breher and co-workers showcased the difficulty of achieving such a transformation.10Herein, we report the oxidative insertion of readily available gold(i) halide precursors into the C–C bond of biphenylene. The appendage of both pyridine and phosphine donors in close proximity to the σC–C bond bridging the two aromatic rings provides additional stabilization to the metal center and results in a de novo entry to cyclometalated (N^C^C)- and (P^C)gold(iii) complexes (Scheme 1b).Our study commenced with the preparation of 5-chloro-1-pyridino-biphenylene system 2via Pd-catalyzed Suzuki cross coupling reaction between 2-bromo-3-methylpyridine and 2-(5-chlorobiphenylen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 1 (Scheme 2).11 To our delight, the reaction of 2 with gold(i) iodide in toluene at 130 °C furnished complex κ3-(N^C^C)Au(iii)–I 3 in 60% yield.12,13 Complex 3 was isolated as yellow plate-type crystals from the reaction mixture and its molecular structure was unambiguously assigned by NMR spectroscopy, high-resolution mass spectrometry (HR-MS) and crystallographic analysis. Complex 3 exhibits the expected square-planar geometry around the metal center, with a Au–I bond length of 2.6558(3) Å.14 The choice of a neutral weakly bound gold(i)-iodide precursor is key for a successful reaction outcome: similar reactions in the presence of [(NHC)AuCl + AgSbF6] failed to deliver the desired biscyclometalation adducts, as reported by Breher et al. in ref. 10. The oxidative insertion of gold(i) iodide into the four-membered ring of pyridino-substituted biphenylene provides a novel and synthetically efficient entry to κ3-(N^C^C)gold(iii) halides. These species have recently found widespread application as precursors for the characterization of highly labile, catalytically relevant gold(iii) intermediates,15a–d as well as for the preparation of highly efficient emitters in OLEDs.15e–g Previous synthetic routes towards these attractive biscyclometalated gold(iii) systems involved microwave-assisted double C–H functionalization reactions that typically proceed with low to moderate yields.15aOpen in a separate windowScheme 2Synthesis of complex 3via oxidative addition of Au(i) into the C–C bond of pyridine-substituted biphenylene. X-ray structures of complex 3 with atoms drawn using 50% probability ellipsoids. Hydrogen atoms have been omitted for clarity. Additional selected bond distances [Å]: N–Au = 2.126(2), C1–Au = 1.973(2), C2–Au = 2.025(2), Au–I = 2.6558(3) and bond angles [deg]: N–Au–I = 99.25(6), N–Au–C1 = 79.82(9), C1–Au–C2 = 81.2(1), C2–Au–I = 99.73(8). For experimental details, see ESI.†Encouraged by the successful results obtained with the pyridine-substituted biphenylene and considering the prominent use of phosphines in gold chemistry,6,16 we wondered whether the same reactivity would be observed for a P-containing system. To this end, both adamantyl- and tert-butyl-substituted phosphines were appended in C1 position of the biphenylene motif. Starting from 5-chlorobiphenylene-1-carbaldehyde 4, phosphine-substituted biphenylenes 5a and 5b could be accessed in 3 steps (aldehyde reduction to the corresponding alcohol, Appel reaction and nucleophilic displacement of the corresponding benzylic halide) in 64 and 57% overall yields, respectively.13 The reactions of 5a and 5b with commercially available gold(i) halides (Me2SAuCl and AuI) furnished the corresponding mononuclear complexes 7a–b and 8a–b, respectively (Scheme 3).13 All these complexes were fully characterized and the structures of 7a, 7b and 8a were unambiguously characterized by X-ray diffraction analysis.13 Interestingly, the nature of the halide has a clear effect on the chemical shift of the phosphine ligand so that a Δδ of ca. 5 ppm can be observed in the 31P NMR spectra of 7a–b (Au–Cl) compared to 8a–b (Au–I), the latter being the more deshielded. The Au–X bond length is also impacted, with a longer Au–I distance (2.5608(1) Å for 8a) compared to that measured in the Au–Cl analogue (2.2941(7) Å for 7a) (Δd = 0.27 Å).13Open in a separate windowScheme 3Synthesis and reactivity of complexes 7a–b, 8a–b, 9 and 10. X-ray structure of complexes 11b, 12 and 14 with atoms drawn using 50% probability ellipsoids. Hydrogen atoms have been omitted for clarity. For experimental details and X-ray structures see ESI.†Despite numerous attempts to promote the C–C activation in these complexes,10,13 all reactions resulted in the formation of highly stable cationic species 11a–b and 12, which could be easily isolated from the reaction media. In the case of cationic mononuclear-gold(i) complexes 11, a ligand scrambling reaction in which the chloride ligand is replaced by a phosphine in the absence of a scavenger, a process previously described for gold(i) species, can be used to justify the reaction outcome.17 The formation of dinuclear gold complex 12 can be ascribed to the combination of a strong aurophilic interaction between the two gold centers (Au–Au = 2.8874(4) Å) and the stabilizing η2-coordination of the metal center to the aromatic ring of biphenylene. Similar η2-coordinated gold(i) complexes have been reported but, to the best of our knowledge, only as mononuclear species.18Taking into consideration the observed geometry of complexes 7a–b in the solid state,13 the facile formation of stable cationic species 11 and 12 and the lack of reactivity of the gold(i) iodides 8a–b, we hypothesized that the free rotation around the C–P bond was probably restricted, placing the gold(i) center away from the biphenylene system and thus preventing the desired oxidative insertion reaction. To overcome this problem, we set out to elongate the arm bearing the phosphine unit with an additional methylene group, introduced via a Wittig reaction from compound 4 to yield ligand 6, prepared in 4 steps in 27% overall yield. Coordination with Me2SAuCl and AuI resulted in gold(i) complexes 9 and 10, respectively (Scheme 3). The structure of 9 was unambiguously assigned by X-ray diffraction analysis and a similar environment around the metal center to that determined for complex 7a was observed for this complex.13With complexes 9 and 10 in hand, we explored their reactivity towards C–C activation of the four-membered ring of biphenylene.19 After chloride abstraction and upon heating at 100 °C for 5 hours, ring opening of the biphenylene system was observed for complex 9. Interestingly, formation of mono-cyclometalated adduct 13 was exclusively observed (the structure of 13 was confirmed by 1H, 13C, 31P, 19F, 11B and 2D NMR spectroscopy and HR-MS).13 The solvent appears to play a major role in this process, as performing the reaction in non-chlorinated solvents resulted in stable cationic complexes similar to 11.13,20,21 The presence of adventitious water is likely responsible for the formation of the monocyclometalated (P^C)gold(iii) complex 13 as when the reaction was carried out in C2H4Cl2 previously treated with D2O, the corresponding deuterated adduct 13-d could be detected in the reaction media. These results showcase the difficulties associated with the biscyclometalation for P-based complexes as well as the labile nature of the expected biscyclometalated adducts. Interestingly though, these processes can be seen as a de novo entry towards relatively underexplored (P^C)gold(iii) species.22The C–C activation was further confirmed by X-ray diffraction analysis of the phosphonium salt 14, which arise from the reductive elimination at the gold(iii) center in 13 upon exchange of the BF4− counter-anion with the weakly coordinating sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF).13,23 The phosphorus atom is four-coordinate, with weak bonding observed to the distant counter-anion and a distorted tetrahedral geometry (C1–P–C2 = 95.05(17), C2–P–C3 = 112.1(1), C3–P–C4 = 116.6(1), C4–P–C1 = 107.4(2) deg). These results represent the third example in which the C(sp2)–P bond reductive elimination at gold(iii) has been reported.24Further, it is important to note that, in contrast to the reactivity observed for the pyridine-substituted biphenylene, neither P-coordinated gold(i) iodo complexes 8a, 8b nor 10 reacted to give cyclometalated products despite prolonged heating, which highlights the need for highly reactive cationized gold(i) species to undergo oxidative addition when phosphine ligands are flanking the C–C bond.13To get a deeper understanding on the observed differences in reactivity for the N- vs. P-based directing groups, ground- and transition-state structures for the oxidative insertion of gold(i) halides in C1-substituted biphenylenes were computed by DFT calculations. The reactions of Py-substituted 2 with AuI to give 3 (I) and those of P-substituted 7a (II) and 9 (III) featuring the cationization of the gold(i) species were chosen as models for comparative purposes with the experimental conditions (Fig. 1 and S1–S10 in the ESI†).25–27 The computed activation energies for the three processes are in good agreement with the experimental data. The pyridine-substituted biphenylene I exhibits the lowest activation barrier for the oxidative insertion process (ΔG‡ = 34.4 kcal mol−1). The reaction on the phosphine-substituted derivatives II and III proved to be, after cationization of the corresponding gold(i) halide complexes (II-BF4, III-BF4) higher in energy (ΔG‡ = 39.6 and 46.3 kcal mol−1 respectively), although the obtained values do not rule out the feasibility of the C–C activation process. The transition state between I and I′ exhibits several interesting geometrical features: (a) the biphenylene is significantly bent, (b) the cleavage of the C–C bond is well advanced (dC–C = 1.898 Å in TSIvs. dC–C = 1.504 Å in I), and (c) the two C and the I atoms form a Y-shape around gold with minimal coordination from the pyridine (dN–Au = 2.742 Å in TSIvs. dN–Au = 2.093 Å in I and 2.157 Å in I′, respectively). The transition-state structures found for the P-based ligands (TSII and TSIII) also show an elongation of the C–C bond and display a bent biphenylene. However, much shorter P–Au distances (dP–Au = 2.330 Å for TSII and 2.314 Å for TSIII) can be observed compared to the pyridine-based system, as expected due to the steric and electronic differences between these two coordinating groups. Analogously, longer C–Au distances were also found for the P-based systems (dC1–Au = 2.152 Å for TSIvs. 2.235 Å and 2.204 Å for TSII and TSIII; dC2–Au = 2.143 Å for TSIvs. 2.219 Å and 2.162 Å for TSII and TSIII), with a larger deviation of square planarity for Au in TSIII compared to TSII.28,29 These results suggest that, provided the appropriate distance to the C–C bond is in place, the strong coordination of phosphorous to the gold(i) center does not prevent the C–C activation of biphenylene but other reactions (i.e. formation of diphosphine gold(i) cationic species, protodemetalation) can outcompete the expected biscyclometalation process. In contrast, a weaker donor such as pyridine offers a suitable balance bringing the gold in close proximity to the C–C bond and enables both the oxidative cleavage as well as the formation of the double metalation product.Open in a separate windowFig. 1Energy profile (ΔG and ΔG‡ in kcal mol−1), optimized structures, transition states computed at the IEFPCM (toluene/1,2-dichloroethane)-B3PW91/DEF2QZVPP(Au,I)/6-31++G(d,p)(other atoms) level of theory for the C–C activation of biphenylene with gold(i) iodide from I and gold(i) cationic from II and III. Computed structures of the transition states (TSI, TSII and TSIII) and table summarizing relevant distances. 相似文献
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Jos García-Calvo Javier Lpez-Andarias Jimmy Maillard Vincent Mercier Chlo Roffay Aurlien Roux Alexandre Fürstenberg Naomi Sakai Stefan Matile 《Chemical science》2022,13(7):2086
HydroFlippers are introduced as the first fluorescent membrane tension probes that report simultaneously on membrane compression and hydration. The probe design is centered around a sensing cycle that couples the mechanical planarization of twisted push–pull fluorophores with the dynamic covalent hydration of their exocyclic acceptor. In FLIM images of living cells, tension-induced deplanarization is reported as a decrease in fluorescence lifetime of the dehydrated mechanophore. Membrane hydration is reported as the ratio of the photon counts associated to the hydrated and dehydrated mechanophores in reconvoluted lifetime frequency histograms. Trends for tension-induced decompression and hydration of cellular membranes of interest (MOIs) covering plasma membrane, lysosomes, mitochondria, ER, and Golgi are found not to be the same. Tension-induced changes in mechanical compression are rather independent of the nature of the MOI, while the responsiveness to changes in hydration are highly dependent on the intrinsic order of the MOI. These results confirm the mechanical planarization of push–pull probes in the ground state as most robust mechanism to routinely image membrane tension in living cells, while the availability of simultaneous information on membrane hydration will open new perspectives in mechanobiology.HydroFlippers respond to membrane compression and hydration in the same fluorescence lifetime imaging microscopy histogram: the responses do not correlate.The detection and study of membrane mechanics in living cells is a topic of current concern.1–14 To enable this research, appropriate chemistry tools, that is small-molecule fluorescent probes that allow imaging of membrane tension, are needed.15 With the direct imaging of physical forces being intrinsically impossible, design strategies toward such probes have to focus on the suprastructural changes caused by changes in membrane tension.15 These suprastructural changes are divers, often interconnected, and vary with the composition of the membrane.15–25 Beyond the fundamental lipid compression and decompression, they include changes in membrane curvature, from rippling, buckling and budding to tubules extending from the membrane and excess lipid being ejected. Of similar importance are changes in membrane organization, particularly tension-induced phase separation and mixing, i.e. assembly and disassembly of microdomains. Consequences of these suprastructural changes include microdomain strengthening and softening and changes in membrane hydration and viscosity.16–25The currently most developed fluorescent flipper probes have been introduced26,27 to image membrane tension by responding to a combination of mechanical compression and microdomain assembly in equilibrium in the ground state.15 Extensive studies, including computational simulations,28 have shown that flipper probes align non-invasively along the lipid tails of one leaflet and report changes in membrane order and tension as changes in fluorescent lifetimes and shifts of excitation maxima.15 Among other candidates, solvatochromic probes respond off-equilibrium in the excited state to changes in membrane hydration and have very recently been considered for the imaging of membrane tension in living cells.29–36 So far not considered to image tension, ESIPT probes also report off equilibrium in the excited state on membrane hydration, but for different reasons.37,38 Mechanosensitive molecular rotors respond off equilibrium in the excited state to changes in microviscosity.17,30,32,39–53 The same principle holds for the planarization of bent, papillon or flapping fluorophores.54–57 The response of all possible probes to tension can further include less desired changes in positioning and partitioning between different domains, not to speak of more catastrophic probe aggregation, precipitation, disturbance of the surrounding membrane structure, and so on. Although the imaging of membrane tension is conceivable in principle with most of above approaches, the complex combination of parameters that has to be in place can thus far only be identified empirically, followed by much optimization.15The force-induced suprastructural changes are accompanied by the alteration in several unrelated physical properties of membranes. It is, for instance, well documented that membrane hydration increases with membrane disorder, from solid-ordered (So) to liquid-disordered (Ld) phases.29,58 Increasing cholesterol content decreases membrane hydration in solid- and liquid-ordered membranes.59 However, studies in model membranes also indicate that membrane hydration and membrane fluidity do not necessarily correlate.59 The dissection of the individual parameters contributing to the response of fluorescent membrane tension probes would be important for probe design and understanding of their responses, but it remains a daunting challenge. In this study, we introduce fluorescent flipper probes that simultaneously report on mechanical membrane compression and membrane hydration at equilibrium in the ground state. Changes of both in response to changes in membrane tension and membrane composition are determined in various organelles in living cells.The dual hydration and membrane tension probes are referred to as HydroFlippers to highlight the newly added responsiveness to membrane hydration. The mechanosensing of lipid compression in bilayer membranes by flipper probes has been explored extensively.15 Fluorescent flippers27 like 1 are designed as bioinspired60 planarizable push–pull probes26 (Fig. 1). They are constructed from two dithienothiophene fluorophores that are twisted out of co-planarity by repulsion of methyls and σ holes on sulfurs61,62 next to the twistable bond. The push–pull system is constructed first from formal sulfide and sulfone redox bridges in the two twisted dithienothiophenes. These endocyclic donors and acceptors are supported by exocyclic ones, here a trifluoroketone acceptor and a triazole donor.63 To assure stability, these endo- and exocyclic donors are turned off in the twisted ground state because of chalcogen bonding and repulsion, respectively.62Open in a separate windowFig. 1The dual sensing cycle of HydroFlippers 1–5, made to target the indicated MOIs in living cells and responding to membrane compression by planarization and to membrane hydration by dynamic covalent ketone hydration. With indication of excitation maxima (ref. 63) and fluorescence lifetimes (this study).Mechanical planarization of the flipper probe establishes conjugation along the push–pull systems, electrons flow from endocyclic donors to acceptors, which turns on the exocyclic donors and acceptors to finalize the push–pull system.62 This elaborate, chalcogen-bonding cascade switch has been described elsewhere in detail, including high-level computational simulations.62 The planar high-energy conformer 1dp excels with red shifted excitation and increased quantum yield and lifetime compared to the twisted conformer 1dt because the less twisted Franck-Condon state favors emission through planar intramolecular charge transfer (PICT) over non-radiative decay through twisted ICT, or conical intersections.15Flipper probe 1 was considered for dual responsiveness to membrane tension and hydration because of the trifluoroketone acceptor.63 Dynamic covalent hydration of 1dt yields hydrate 1ht.64–76 Blue-shifted excitation and short lifetime of 1ht are not expected to improve much upon planarization because the hydrate is a poor acceptor and thus, the push–pull system in 1hp is weak. The dynamic covalent chemistry of the trifluoroketone acceptor has been characterized in detail in solution and in lipid bilayer membranes.63To explore dual responsiveness to membrane tension in any membrane of interest (MOI) in living cells, HydroFlippers 2–5 were synthesized. While HydroFlipper 1 targets the plasma membrane (PM), HydroFlippers 2–4 were equipped with empirical targeting motifs.77 HydroFlipper 5 terminates with a chloroalkane to react with the self-labeling HaloTag protein, which can be expressed in essentially any MOI.78 Their substantial multistep synthesis was realized by adapting reported procedures (Schemes S1–S4†).The MOIs labeling selectivity of HydroFlippers was determined in HeLa Kyoto (HK) cells by confocal laser scanning microscopy. Co-localization experiments of flippers 1–4 with the corresponding trackers gave Pearson correlation coefficients (PCCs) >0.80 for the targeting of mitochondria, lysosomes and the endoplasmic reticulum (ER, Fig. S4–S6†). HydroFlipper 5 was first tested with stable HGM cells, which express both HaloTag and GFP on mitochondria (referred to as 5M).78,79 The well-established chloroalkane penetration assay demonstrated the efficient labeling of HaloTag protein by 5 as previously reported HaloFlippers (Fig. S3†).78 By transient transfection, HydroFlippers 5 were also directed to lysosomes (5L), Golgi apparatus (GA, 5G)80 and peroxisomes (5P) with HaloTag and GFP expressed on their surface.78 PCCs >0.80 for co-localization of flipper and GFP emission confirmed that MOI labeling with genetically engineered cells was as efficient as with empirical trackers (Fig. S7–S11†).Dual imaging of membrane compression and hydration was envisioned by analysis of fluorescence lifetime imaging microscopy (FLIM) images using a triexponential model (Fig. 2).81 FLIM images of ER HydroFlipper 4 in iso-osmotic HK cells were selected to illustrate the concept (Fig. 3a). Contrary to classical flipper probes, the fluorescence decay curve of the total FLIM image (Fig. 2a, grey) showed a poor fit to a biexponential model (Fig. 2a, cyan, b). Consistent with their expected dual sensing mode, a triexponential fit was excellent (Fig. 2a, dark blue, c). Lifetimes τ1i = 4.3 ns (†) were obtained besides background. This three-component model was then applied to every pixel of FLIM images (Fig. 3c). The resulting reconvoluted FLIM histogram revealed three clearly separated populations for τ1 (red), τ2 (green), and background (τ3, blue, Fig. 2d). Maxima of these three clear peaks were at the lifetimes estimated by triexponential fit of the global decay curve, thus demonstrating the validity of the methodology at necessarily small photon counts. Irreproducible fitting would give randomly scattered data without separated peaks.Open in a separate windowFig. 2(a) Fluorescence decay curve (grey, corresponding to the total image, not to a single pixel) with biexponential (cyan) and triexponential fit (dark blue). (b, c) Residual plots for bi- (b) and triexponential fit (c). (d) Histogram with the intensities associated with the τ1 (red), τ2 (green), and τ3 (blue, background) components obtained by triexponential fit of the fluorescence decay curve of each pixel of the FLIM image, fit to Gaussian function (black solid curves).Open in a separate windowFig. 3FLIM images of HK cells labelled with ER flipper 4 before (a, c) and after (b, d) hyper-osmotic shock, showing average lifetimes τav (a, b) and τ1 (c, d) from triexponential reconvolution; scale bars = 10 μm. (e) Distribution of the photon counts associated with the τ1 component of 4 in HK cells after triexponential reconvolution of FLIM images before (c, τ1i) and after (d, τ1h) hyper-osmotic shock, showing decreasing lifetimes for τ1 (4d). (f) The dehydration factor dhi defined as total integrated photon counts for τ1 (Στ1) divided by Στ2 (i.e., dhi = area Στ1i/area Στ2i) for 4 in strongly hydrated ER (dhi < 2, turquoise) and 1 in weakly hydrated plasma membrane (dhi > 6, purple) of HK Kyoto cells under iso-osmotic conditions.Dual response of HydroFlippers to changes in membrane tensiona
Open in a separate windowaFrom triexponential fit of FLIM images in HK cells (errors, see ESI).bFlipper (target MOI).cdhi = area Στ1i/area Στ2i in FLIM histogram under iso-osmotic (i) conditions (e.g.Fig. 3f).ddhh = area Στ1h/area Στ2h in FLIM histogram under hyper-osmotic (h) conditions.eFlipper hydration change in response to membrane tension: Δdh = (1 – dhh/dhi) × 100%.fFluorescence lifetime value of the slowest component from the fitted fluorescence decay under iso-osmotic (i) conditions (e.g.Fig. 2d).gSame as f, under hyper-osmotic (h) conditions.hFlipper planarization in response to membrane tension: Δτ1 = (1 – τ1h/τ1i) × 100%.iMeasured after cholesterol (C) removal from cells with MβCD.jCompared to dhi of 1 (6.6) in untreated cells measured on the same day.kCompared to τih of 1 (5.0) in untreated cells measured on the same day.lAs j using 4 and compared to dhi = 1.8.mAs k using 4 compared to τih = 4.5.nMeasured in transiently transfected HK cells with ST-HaloTag-HA expressed inside GA.80oMeasured in transiently transfected HK cells with HaloTag-Sec61B expressed inside ER.78pMeasured in SM/C GUVs.qMeasured in DOPC GUVs.Extensive lifetime data for monofunctional flipper probes supported that the intensities associated to τ1i (i for iso-osmotic, see below) originate from at least partially planarized flippers 4d in the ER (Fig. 2d, red, 3c, 1). The population of the τ2i component in the reconvoluted FLIM histogram was attributed to the presence of hydrated 4h in the ER (Fig. 2d, green, 1). This assignment was consistent with lifetime differences in solution between τ = 2.7 ns for the dehydrated and τ = 0.7 ns for the hydrated form of a hydrophobic flipper analog in dioxane-water mixtures (Fig. S2†), and model studies in GUVs (see below).63The ratio between the τ1i (red) and τ2i (green) populations in the reconvoluted FLIM histogram was used to extract a quantitative measure for hydration of the MOI (Fig. 2d, ,3f).3f). A dehydration factor dh was defined by dividing the total integrated counts for τ1 (Στ1) by Στ2. For 4 in iso-osmotic ER, dhi = 1.8 ± 0.1 was obtained (Fig. 3f, †63 Thus, these results implied that the dehydration factor dh obtained from reconvoluted triexponential FLIM images reports quantitatively on membrane hydration, that is the local water concentration around HydroFlippers in their MOI.In uniform model membranes composed of only one lipid, flipper probes like 1 respond to increasing membrane tension with decreasing lifetimes.15,18 This response can be explained by flipper deplanarization upon lipid decompression. In the mixed membranes composed of different lipids, flipper probes reliably respond to increasing membrane tension with increasing lifetimes, and lifetime changes can be calibrated quantitatively to the applied physical force.18,77 This indicates that in these biologically relevant membranes, the response is dominated by factors other than lipid decompression. Tension-induced microdomain formation is confirmed to account for, or at least contribute to, increasing lifetimes with increasing tension, or membrane decompression.15,18 Not only microdomain disassembly but also changes in membrane curvature from rippling, budding and microdomain softening to tube formation and lipid ejection combine to afford decreasing lifetimes with membrane compression, or decreasing tension.17,18Membrane tension was applied to the ER by extracellular hyper-osmotic stress. This causes membrane tension to decrease, i.e., membrane compression to increase.18,77 Consistent with tension-induced deplanarization from 4p to 4t (Fig. 1), lifetimes of 4 visibly decreased in response to decreasing membrane tension (Fig. 3b). The reconvoluted FLIM histogram clearly shows that compression caused the decrease of τ1 of 4 in the ER from τ1i = 4.3 ns to τ1h = 3.7 ns, whereas τ2i = 1.5 ns was less mechanosensitive (τ2h = 1.4 ns, Fig. 3e, 4a–c). These different mechanosensitivities were meaningful considering that in three-component histograms, τ1 originates from dehydrated HydroFlipper 4d that loses a strong push–pull dipole and thus shortens lifetime upon tension-induced deplanarization from 4dp to 4dt (Fig. 1). In contrast, hydrated HydroFlipper 4h accounting for τ2 lacks a strong dipole and thus features short lifetimes with poor sensitivity for tension-induced deplanarization from 4hp and 4ht. This result was consistent with the central importance of turn-on push–pull systems for flipper probes to function as mechanosensitive planarizable push–pull probes.81Open in a separate windowFig. 4(a) Reconvoluted FLIM histograms for 1–5 obtained by fitting each pixel of the FLIM image to a three-exponential model under iso-osmotic (top) and hyper-osmotic (bottom) conditions in HK cells; *dhi analysis in Fig. 3f; **Δτ1 analysis in Fig. 3e. (b–e) Trend plots for membrane compression (τ1) and hydration (dh) for 1–5 in HK cells without (b, e) and in response to hyper-osmotic membrane tension (c–e). (b) τ1i (iso-osmotic compression) vs. dhi (iso-osmotic hydration). (c) τ1i–τ1hvs. τ2i–τ2h (compression response in ns). (d) Δτ1 (compression response, %) vs. Δdh (hydration response, %), (e) Δτ1 and Δdh upon compression (σ) and cholesterol depletion (C). #Discontinuous, see 17,18The uniform response of HydroFlipper planarization and hydration thus provided corroborative support that membrane deformation and reorganization dominate the fluorescence imaging of membrane tension under the condition that the probe partitions equally between different phases.63 However, the dual response HydroFlipper dissects the consequences of these tension-induced suprastructural changes. HydroFlipper planarization 4t/4p detected by τ1 reports on lipid compression in the local environment in the MOI. HydroFlipper hydration 4d/4h detected by the dehydration factor dh reports on local membrane hydration. Pertinent reports from model membranes in the literature indicate that the two do not have to be the same.59To elaborate on these implications, FLIM images were recorded for all HydroFlippers 1–5 in their respective MOIs before and after the application of hyper-osmotic stress and then analyzed using the three-component model (Fig. 4a, Fig. 4a) and estimated by global triexponential fit (Fig. 3f, ,4a).4a). However, these changes do not affect dhi, which compares areas rather than maxima in the histograms.Trends for membrane hydration and compression reported by dhi and τ1i, respectively, should reflect the overall composition and thus nature of the different membranes. For PM 1, Lyso 2, GA 5G and ER 5E, coinciding trends were found for hydration (dhi, blue) and compression (τ1i, red, Fig. 4b). Hydration and deplanarization increased in parallel, consistent with increasingly disordered membranes. With Mito 3 and ER 4, increasing hydration (blue) was not reflected in increasing deplanarization (red, Fig. 4b).For the comprehensive analysis of the changes caused by hyper-osmotic stress, the differences in lifetimes for τ1 and τ2 were clarified first. Whereas τ1i–τ1h values (red) around 0.3 ns were large and significant in all MOIs, τ2i–τ2h values (pink) were negligible (Fig. 4c). The mechano-insensitive τ2, corresponding to hydrate 4h, were thus not further considered as a valid measure of membrane compression.To facilitate direct comparability, membrane compression Δτ1 and membrane dehydration Δdh in response to hyper-osmotic stress were converted in percentage of decrease (positive) or increase (negative) from the value under iso-osmotic conditions (Fig. 4d, Fig. 4d, red). In clear contrast, dehydration Δdh varied from 3% increase to 29% decrease (Fig. 4d, blue). The most extreme deviations concerned ER probes with maximal Δτ1 responsiveness for tracker 4 and minimal Δτ1 responsiveness for Halo flipper 5E. For dehydration Δdh, both probes showed high responsiveness. These extremes could reflect the diverse membrane properties of the ER, with τ = 4.1, 3.5 and 3.4 ns reported previously for different flipper mechanophores in tubular, sheet, and nuclear membranes of COS7 cells, respectively.15,77 Although less resolvable in HK cells, this heterogeneity of ER membranes is also visible in the FLIM images with 4 (Fig. 3). Tracker 4 and Halo flipper 5E both react covalently with membrane proteins and report on the respective surrounding ER membrane, which differs significantly according to the two HydroFlipper probes. The extreme values for Halo flipper 5E suggested that other factors like fractions of mispositioned flipper in more hydrophilic environment could also contribute to the global outcome (Fig. 4b, Fig. 4d, blue) increased with membranes disorder characterized by shorter τ1i and low dhi (Fig. 4b), while Δτ1 remained more constant until the possible onset of decreases at very high hydration (5E, Fig. 4d, red). Both observations - independence of mechanical flipper planarization and dependence of dynamic covalent hydrate formation on the water concentration in the surrounding membrane - were chemically meaningful.The validity of these conclusions was tested by removing cholesterol with methyl-β-cyclodextrin (MβCD). As expected for the increased hydration level and decreased order of cholesterol depleted membranes, Δdh and Δτ1 of 1 and 4 increased by MβCD treatment compared to those obtained on the same day without the treatment (Fig. 4e, C). Stronger response of ER HydroFlipper 4 to the cholesterol removal can be attributed to the poorer cholesterol content in ER membranes than in PM.82 Consistent with the overall trend, Δdh was more significantly affected by changes of the MOI by MβCD treatment than by tension change (Fig. 4e, blue, C vs. σ), while Δτ1 responded better to membrane tension than MOI change (Fig. 4e, red, C vs. σ).Taken together, these results reveal HydroFlippers as first dual mode fluorescent membrane tension probe, reporting on membrane hydration and membrane compression at the same time. Mechanical compression is reported as shift in τ, while tension-induced hydration is reported as change in relative photon counts for hydrated and dehydrated probes in the reconvoluted FLIM histograms. The response of flipper deplanarization to membrane tension is robust and less dependent on the nature of the MOI, including plasma membrane, ER, mitochondria, lysosomes and Golgi. In contrast, the responsiveness of flipper hydration to membrane tension depends strongly on the nature of the MOI, generally increasing with increasing intrinsic disorder, that is hydration, already under iso-osmotic conditions. These results validate the flipper probes as most reliable to routinely image membrane tension in cells, while the simultaneous information provided on membrane dehydration provides attractive possibilities for biological applications. 相似文献
Probeb | dhic | dhhd | Δdhe (%) | τ 1i f (ns) | τ 1h g (ns) | Δτ1h (%) | |
---|---|---|---|---|---|---|---|
1 | 1 (PM) | 6.3 | 6.5 | -3 | 4.8 | 4.4 | 8 |
2 | 1 (-C)i | 6.1 | — | 8j | 4.8 | — | 3k |
3 | 2 (Lyso) | 2.9 | 2.8 | 4 | 4.4 | 4.0 | 10 |
4 | 3 (Mito) | 2.3 | 1.9 | 17 | 4.4 | 4.0 | 8 |
5 | 4 (ER) | 1.8 | 1.5 | 17 | 4.3 | 3.7 | 15 |
6 | 4 (–C)i | 1.1 | — | 39l | 4.1 | — | 10m |
7 | 5G (GA)n | 2.5 | 2.3 | 8 | 4.2 | 3.8 | 10 |
8 | 5E (ER)o | 1.7 | 1.2 | 29 | 3.8 | 3.7 | 5 |
9 | 1 (Lo)p | 11 | — | — | 5.2 | — | — |
10 | 1 (Ld)q | 1.2 | — | — | 3.4 | — | — |
9.
Described herein is a dirhodium(ii)-catalyzed asymmetric cycloisomerization reaction of azaenyne through a cap-tether synergistic modulation strategy, which represents the first catalytic asymmetric cycloisomerization of azaenyne. This reaction is highly challenging because of its inherent strong background reaction leading to racemate formation and the high capability of coordination of the nitrogen atom resulting in catalyst deactivation. Varieties of centrally chiral isoindazole derivatives could be prepared in up to 99 : 1 d.r., 99 : 1 er and 99% yield and diverse enantiomerically enriched atropisomers bearing two five-membered heteroaryls have been accessed by using an oxidative central-to-axial chirality transfer strategy. The tethered nitrogen atom incorporated into the starting materials enabled easy late-modifications of the centrally and axially chiral products via C–H functionalizations, which further demonstrated the appealing synthetic utilities of this powerful asymmetric cyclization.Rh(ii)-catalyzed asymmetric cycloisomerization of azaenyne through a cap-tether synergistic modulation strategy was described. Diverse centrally and axially chiral isoindazoles were prepared and directed C–H late-stage modifications were developed.Known as one of the most significant and reliable access methods to chiral heterocycles, asymmetric cycloisomerization of conjugated enyne has caught extensive attention and interest for its wide applications in synthetic route design and mechanistic investigation.1 Specifically, asymmetric cyclization of conjugated enynone (X = C, Z = O) has been successfully developed and applied to the rapid construction of various chiral furan-containing skeletons with high efficiency in an extremely operationally simple manner (Scheme 1a).2 However, compared to the fruitful research with enynone, it is surprising that the analogous asymmetric version of azaenyne (Z = N–R) still remains underdeveloped.3 In fact, no successful example of catalytic asymmetric cyclization of azaenyne has been reported in the literature despite the apparent significance of nitrogen-containing five-membered heterocycles in the synthetic and pharmaceutical community.4 In 2004, Haley and Herges reported a detailed experimental and theoretical study of the cyclization reaction of (2-ethynylphenyl)-phenyldiazene, which is a unique azaenyne.5 According to the DFT calculations, very close and low activation barriers for 5-exo-dig and 6-endo-dig cyclization pathways under catalyst-free conditions were found, which shed light on the inherent challenges of the asymmetric reaction of azaenyne (Scheme 1b). For instance, there was usually a regioselectivity issue (5-exo and 6-endo) in the cyclization reaction of azaenyne because of their close reaction barriers where the competitive 6-endo-dig cyclization3a,6 may lead to troublesome side-product formation. In addition, the low activation barrier deriving from the strong N-nucleophilicity of azaenyne may easily lead to self-cyclization which will cause severe background reactions to interfere with the asymmetric process. More troublingly, this transformation might suffer from catalyst deactivation arising from the high coordinating capability of the nitrogen atom in both starting materials and products, which might give more opportunities to the propagation of detrimental background reactions. In some cases, even a super-stoichiometric amount of transition metal has to be used to ensure effective conversion.3a,7 Therefore, although many nonchiral approaches have been reported,3,5 catalytic asymmetric cyclization of azaenyne still remains elusive due to the inherent obstacles aforementioned. With our continuous interest in alkyne chemistry,2a,8 herein we designed a cap-tether synergistic modulation strategy to tackle these challenges, envisioning that modulation of the tethered atom and protecting cap of nitrogen in the azaenyne would intrinsically perturb and alter the reactivity of the starting material, and therefore the azaenyne motif could be effectively harnessed as a promising synthon for asymmetric transformations (Scheme 1c). It should be noted that the obtained centrally chiral product produced from intramolecular C–H insertion of donor-type metal carbene9 might be potentially converted into the axially chiral molecule via a central-to-axial chirality conversion strategy.Open in a separate windowScheme 1Development of the asymmetric cyclization reaction of conjugated azaenyne.With this design in mind, different types of azaenynes bearing typical tethering atoms and capping groups were chosen to test our hypothesis and representative results are shown in Scheme 2. First, tBu-capping imine (X = C, R = tBu) was selected as a substrate to test our hypothesis.6a It was found that the imine exhibited low reactivity and the reaction temperature has to be elevated to 100 °C to initiate the transformation with or without catalyst. Unfortunately, the desired 5-exo-dig cyclization product was not detected, but isoquinoline from 6-endo-dig cyclization was obtained instead (Scheme 2a). To further regulate and control the regioselectivity and reactivity, triazene (X = N, R = N-piperidyl) was then investigated. Similarly, this substrate also showed low reactivity and it is still required to be heated at 100 °C for conversion. In the absence of a metal catalyst, an unexpected alkyne, deriving from the fragmentation of the triazene moiety, was produced in 41% yield. When 2 mol% Rh2(OPiv)4 was added as a catalyst, the side reaction could be efficiently suppressed and the reaction selectivity was apparently reversed. In this case, the target C–H insertion dihydrofuran was furnished as the major product in 30% yield but still accompanied by concomitant formation of 12% yield of undesired alkyne (Scheme 2b). The above investigations showed neither the imine nor triazene was an ideal substrate for the asymmetric reaction. Thus, we moved our attention to the diazene substrate (X = N, R = aryl). As demonstrated by Haley''s and Herges'' pioneering work, ortho-alkynyl diazene, compared with imine and triazene, was more unstable and tended to self-cyclization even at room temperature.5a As shown in Scheme 2c, the ortho-alkynyl diazene degrades and 5-exo-dig cyclization products could be observed even in DCE solvent without any catalyst at room temperature. When the phenyl capping group was installed in the substrate, the reaction furnished 10% yield of isoindazole derivative. The uncatalyzed self-cyclization reaction was obviously accelerated when an electron-rich capping group (4-MeO–C6H4–) was introduced, affording the corresponding product in 20% yield. Inspired by these findings, we assumed that installation of an electron deficient group on the capping phenyl would reduce the nucleophilicity of the nitrogen atom and thus the troublesome self-cyclization reaction might be effectively inhibited. To our delight, when a bromo-substituent was introduced onto the phenyl cap, the undesired self-cyclization was almost suppressed. When Rh2(OPiv)4 was added as a catalyst, the desired carbene-involved C–H insertion product was furnished in 90% yield at room temperature. Worthy of note was the total absence of any cinnoline formation from 6-endo-dig cyclization.3a,6b In short, the synthetic challenges associated with regioselectivity (5-exo-dig and 6-endo-dig), strong background reaction and catalyst deactivation could be successfully regulated and controlled via a tether-cap synergistic modulation strategy.Open in a separate windowScheme 2Typical substrate investigation.Encouraged by the above findings, ortho-alkynyl bromodiazene 1a was chosen as a model substrate and different types of chiral dirhodium catalysts10 were screened in DCE at room temperature for 48 h. As shown in Entry Rh(ii)* Solvent Yieldb [%] erc 1 Rh2(R-DOSP)4 DCE 56 29 : 71 2 Rh2(5S-MEPY)4 DCE 17 50 : 50 3 Rh2(S-BTPCP)4 DCE 61 8 : 92 4 Rh2(S-PTPA)4 DCE 91 91 : 9 5 Rh2(S-PTTL)4 DCE 86 97 : 3 6 Rh2(S-PTAD)4 DCE 93 94 : 6 7 Rh2(S-NTTL)4 DCE 92 96 : 4 8 Rh2(S-TCPTTL)4 DCE 95 98 : 2 9 Rh 2 (S-TFPTTL) 4 DCE 98 d 98 : 2 10 Rh2(S-TFPTTL)4 DCM 88 98 : 2 11 Rh2(S-TFPTTL)4 Toluene 92 98 : 2 12 Rh2(S-TFPTTL)4 MeCN 16 92 : 8 13 Rh2(S-TFPTTL)4 n-Hexane 96 98 : 2 14e Rh2(S-TFPTTL)4 DCE 65f 96 : 4