Multistep energy and electron transfer processes in novel rotaxane donor–acceptor hybrids generating microsecond-lived charge separated states

A new set of [Cu(phen)₂]⁺ based rotaxanes, featuring [60]-fullerene as an electron acceptor and a variety of electron donating moieties, namely zinc porphyrin (ZnP), zinc phthalocyanine (ZnPc) and ferrocene (Fc), has been synthesized and fully characterized with respect to electrochemical and photophysical properties. The assembly of the rotaxanes has been achieved using a slight variation of our previously reported synthetic strategy that combines the Cu(i)-catalyzed azide–alkyne cycloaddition reaction (the “click” or CuAAC reaction) with Sauvage''s metal-template protocol. To underline our results, complementary model rotaxanes and catenanes have been prepared using the same strategy and their electrochemistry and photo-induced processes have been investigated. Insights into excited state interactions have been afforded from steady state and time resolved emission spectroscopy as well as transient absorption spectroscopy. It has been found that photo-excitation of the present rotaxanes triggers a cascade of multi-step energy and electron transfer events that ultimately leads to remarkably long-lived charge separated states featuring one-electron reduced C₆₀ radical anion (C₆₀˙^–) and either one-electron oxidized porphyrin (ZnP˙⁺) or one-electron oxidized ferrocene (Fc˙⁺) with lifetimes up to 61 microseconds. In addition, shorter-lived charge separated states involving one-electron oxidized copper complexes ([Cu(phen)₂]²⁺ (τ < 100 ns)), one-electron oxidized zinc phthalocyanine (ZnPc˙⁺; τ = 380–560 ns), or ZnP˙⁺ (τ = 2.3–8.4 μs), and C₆₀˙^– have been identified as intermediates during the sequence. Detailed energy diagrams illustrate the sequence and rate constants of the photophysical events occurring with the mechanically-linked chromophores. This work pioneers the exploration of mechanically-linked systems as platforms to position three distinct chromophores, which are able to absorb light over a very wide range of the visible region, triggering a cascade of short-range energy and electron transfer processes to afford long-lived charge separated states.     

2,1,3-Benzothiadiazole-containing donor–acceptor–acceptor dyes for dye-sensitized solar cells

A series of organic dyes with a donor–acceptor–acceptor (D–A–A) configuration, in which various diarylthienylamine donors and a cyanoacrylic acid acceptor are bridged by a low-band-gap 2,1,3-benzothiadiazole acceptor, have been synthesized, characterized, and employed as photosensitizers for dye-sensitized solar cells (DSSCs). The adoption of 2,1,3-benzothiadiazole as the bridging acceptor endowed these tailor-made dyes with superior light-harvesting capabilities in comparison to their previously reported pyrimidine-based analogs. After fine-tuning the fabrication conditions, DSSCs based on these dyes showed solar spectral responses extending to the near-IR region and achieved power conversion efficiencies (PCEs) of up to 3.16% (OHexDPTB) under simulated AM 1.5G irradiation (100 mW cm^?2).     

Three-phase junction for modulating electron–hole migration in anatase–rutile photocatalysts

The heterophase solid–solid junction as an important type of structure unit has wide applications for its special mechanics and electronic properties. Here we present a first three-phase atomic model for the anatase–rutile TiO₂ heterophase junction and determine its optical and electronic properties, which leads to resolution of the long-standing puzzles on the enhanced photocatalytic activity of anatase–rutile photocatalysts. By using a set of novel theoretical methods, including crystal phase transition pathway sampling, interfacial strain analysis and first principles thermodynamics evaluation of holes and electrons, we identify an unusual structurally ordered three-phase junction, a layer-by-layer “T-shaped” anatase/TiO₂-II/rutile junction, for linking anatase with rutile. The intermediate TiO₂-II phase, although predicted to be only a few atomic layers thick in contact with anatase, is critical to alleviate the interfacial strain and to modulate photoactivity. We demonstrate that the three-phase junction acts as a single-way valve allowing the photogenerated hole transfer from anatase to rutile but frustrating the photoelectron flow in the opposite direction, which otherwise cannot be achieved by an anatase–rutile direct junction. This new model clarifies the roles of anatase, rutile and the phase junction in achieving high photoactivity synergistically and provides the theoretical basis for the design of better photocatalysts by exploiting multi-phase junctions.     

Enantioselective cis-β-lactam synthesis by intramolecular C–H functionalization from enoldiazoacetamides and derivative donor–acceptor cyclopropenes

β-Lactam derivatives are produced through intermediate donor–acceptor cyclopropene intermediates in high yield, exclusive cis-diastereoselectivity, and high enantiocontrol in a chiral dirhodium carboxylate catalyzed intramolecular C–H functionalization reaction of enoldiazoacetamides.     

Long-range electron and excitation energy transfer in donor–bridge–acceptor systems

Donor–bridge–acceptor (D-B-A) systems, either as supermolecules or on surfaces, have been extensively studied with respect to long-range electron (ET) and excitation energy (EET) transfer. In more recent years, the main research objective has been to develop knowledge on how to construct molecular-based devices, with predetermined electron transfer properties, intended for application in electronics and photovoltaics. At present, such construction is in general hampered for several reasons. Most importantly, the property of a D-B-A system is not a simple linear combination of properties of the individual components, but depends on the specific building blocks and how they are assembled. An important example is the ability of the bridge to support the intended transfer process. The mediation of the transfer is characterized by an attenuation factor, β, often viewed as a bridge specific constant but which also depends on the donor and the acceptor, i.e. the same bridge can either be poorly or strongly conducting depending on the donor and acceptor. This review gives an account of the experimental exploration of the attenuation factor β in a series of bis(porphyrin) systems covalently linked by bridges of the oligo(phenyleneethynylene) (OPE) type. Attenuation factors for ET as well as for both singlet and triplet EET are discussed. A report is also given on the dependence of the transfer efficiency on the energy-gap between the donor and bridge states relevant for the specific transfer process. The experimental variation of β with varying donor and acceptor components is shown for a range of conjugated bridges by representative examples from the literature. The theoretical rationalization for the observed variation is briefly discussed. Based on the Gamow tunneling model, the observed variations in β-values with varying donors and acceptors for the same bridges is simulated successfully simultaneously as the observed energy-gap dependence is modelled.     

Temperature dependence of photoinduced electron transfer in hydrogen-bonded donor–acceptor systems

We have studied the temperature dependence of photoinduced electron transfer (PET) reactions in three hydrogen-bonded donor–acceptor systems in the range 220–298 K. For the hydrogen-bonded system in the normal region, the PET rate constant was found to increase with increase in temperature. For the two systems in the inverted region, the rate constants were nearly independent of temperature. We have analyzed the results using electron transfer theories.     

A carbon–carbon hybrid – immobilizing carbon nanodots onto carbon nanotubes

The thrust of this work is to integrate small and uniformly sized carbon nanodots (CNDs) with single-walled carbon nanotubes (SWCNT) of different diameters as electron donors and electron acceptors, respectively, and to test their synergetic interactions in terms of optoelectronic devices. CNDs (denoted pCNDs, where p indicates pressure) were prepared by pressure-controlled microwave decomposition of citric acid and urea. pCNDs were immobilized on single-walled carbon nanotubes by wrapping the latter with poly(4-vinylbenzyl trimethylamine) (PVBTA), which features positively charged ammonium groups in the backbone. Negatively charged surface groups on the CNDs lead to attractive electrostatic interactions. Ground state interactions between the CNDs and SWCNTs were confirmed by a full-fledged photophysical investigation based on steady-state and time-resolved techniques. As a complement, charge injection into the SWCNTs upon photoexcitation was investigated by ultra-short time-resolved spectroscopy.     

Colorimetric and electrochemical sensing for fluoride anion by ferrocenyl-based imidazole compound with electron donor–acceptor structure

Research on Chemical Intermediates - In this paper, a new ferrocenylimidazole compound L was designed and synthesized. L could selectively sense a fluoride anion among test anions such as F?,...     

Copper-catalyzed intermolecular C(sp3)–H bond functionalization towards the synthesis of tertiary carbamates

We describe the development of an intermolecular unactivated C(sp³)–H bond functionalization towards the direct synthesis of tertiary carbamates. The transformation proceeded using a readily available, abundant first-row transition metal catalyst (copper), and isocyanates as the source of the amide moiety. This is a novel strategy for direct transformation of a variety of unactivated hydrocarbon feedstocks to N-alkyl-N-aryl and N,N-dialkyl carbamates without pre-functionalization or installation of a directing group. The reaction had a broad substrate scope with 3° > 2° > 1° site selectivity. The reaction proceeded even on a gram scale, and a corresponding free amine was directly obtained when the reaction was performed at high temperature. Kinetic studies suggested that radical-mediated C(sp³)–H bond cleavage was the rate-determining step.     

Spectroscopic investigation of novel donor–acceptor chromophores as specific application agents for opto-electronics and photonics

Donor–acceptor chromophores were synthesized by Knoevenagel condensation and characterized by using spectroscopic measurements (FT-IR, ¹H NMR, ¹³C NMR, and mass) and elemental analyses. UV–Vis and fluorescence spectroscopic studies provided that these dyes are good absorbent and fluorescent. The results of photostability study showed that photobleaching of Dyes 2 and 4 was more significant than that of Dyes 1 and 3, providing that Dyes 1 and 3 are more photostable than Dyes 2 and 4. In addition, all dyes included in this study are found to be sensitive to the polarity of the microenvironment provided by different solvents based on the results of fluorescence polarity studies.     

New donor–acceptor copolymers with ultra-narrow band gap for photovoltaic application

Two novel donor–acceptor (D–A) copolymers P1 and P2 with the thiazoloquinoxaline repeating acceptor moiety and different donor moieties of benzo[1,2-b:4,5-b']dithiophene and isomeric benzo[2,1-b:3,4-b']dithiophene have been prepared. The polymers show light absorption at 300–1200 nm and a band gap width of 0.98 and 1.14 eV, respectively. The energies of the HOMO (–5.42 and–5.29 eV) and LUMO (–3.90 and–3.83 eV) levels of polymers P1 and P2 have been determined. The absorption maximum for polymer P1 in the long-wavelength region is red-shifted by 161 nm, which is caused by stronger charge transfer in P1 as compared with P2. This fact indicates that the benzo[1,2-b:4,5-b']dithiophene structural moiety has a higher electron-donating ability than the benzo[2,1-b:3,4-b']dithiophene moiety. The red shift of the absorption spectrum of polymer P1 in comparison with that of P2 indicates that interchain π–π stacking interactions are more efficient in P1 than in P2.     

Nanoscale cooperativity on a series of statistical methacrylates copolymers with electron donor–acceptor pendant groups

Standard and StepScan DSC studies have been performed on a series of statistical methacrylate copolymers with electron-donor and electron-acceptor pendant groups that form intramolecular electron transfers. From standard DSC analysis we concluded that glass transition temperature slowly increased with increasing electron-acceptor monomeric moiety ratio up to 0.5 in the main chain. Using StepScan DSC method we calculated the size and volume of cooperative rearranging region as well mean temperature fluctuation at glass transition temperature. It was estimated also the average number of monomer units in the cooperative rearranging region. All parameters were calculated according to the method proposed by Donth based on Heat Capacity Spectroscopy. The results show that the presence of intermonomeric electron transfers decreased the chain mobility, as well as the cooperativity of relaxation processes of these structures in the glass transition range. This is reflected by minimal values of these parameters around 0.4 ratio of copolymer composition. Such behavior is similar to that of crosslinked or confined systems (e.g., nanocomposites, thin films) that have reduced chain mobility.     

Unveiling the nature of supramolecular crown ether–C60 interactions

A series of exTTF-(crown ether)₂ receptors, designed to host C₆₀, has been prepared. The size of the crown ether and the nature of the heteroatoms have been systematically changed to fine tune the association constants. Electrochemical measurements and transient absorption spectroscopy assisted in corroborating charge transfer in the ground state and in the excited state, leading to the formation of radical ion pairs featuring lifetimes in the range from 12 to 21 ps. To rationalize the nature of the exTTF-(crown ether)₂·C₆₀ stabilizing interactions, theoretical calculations have been carried out, suggesting a synergetic interplay of donor–acceptor, π–π, n–π and CH···π interactions, which is the basis for the affinity of our novel receptors towards C₆₀.     

Heterometallic titanium–gold complexes inhibit renal cancer cells in vitro and in vivo

Following recent work on heterometallic titanocene–gold complexes as potential chemotherapeutics for renal cancer, we report here on the synthesis, characterization and stability studies of new titanocene complexes containing a methyl group and a carboxylate ligand (mba = S–C₆H₄–COO^–) bound to gold(i)-phosphane fragments through a thiolate group [(η-C₅H₅)₂TiMe(μ-mba)Au(PR₃)]. The compounds are more stable in physiological media than those previously reported and are highly cytotoxic against human cancer renal cell lines. We describe here preliminary mechanistic data involving studies on the interaction of selected compounds with plasmid (pBR322) DNA used as a model nucleic acid, and with selected protein kinases from a panel of 35 protein kinases having oncological interest. Preliminary mechanistic studies in Caki-1 renal cells indicate that the cytotoxic and anti-migration effects of the most active compound 5 [(η-C₅H₅)₂TiMe(μ-mba)Au(PPh₃)] involve inhibition of thioredoxin reductase and loss of expression of protein kinases that drive cell migration (AKT, p90-RSK, and MAPKAPK3). The co-localization of both titanium and gold metals (1 : 1 ratio) in Caki-1 renal cells was demonstrated for 5 indicating the robustness of the heterometallic compound in vitro. Two compounds were selected for further in vivo studies on mice based on their selectivity in vitro against renal cancer cell lines when compared to non-tumorigenic human kidney cell lines (HEK-293T and RPTC) and the favourable preliminary toxicity profile in C57BL/6 mice. Evaluation of Caki-1 xenografts in NOD.CB17-Prkdc SCID/J mice showed an impressive tumor reduction (67%) after treatment for 28 days (3 mg per kg per every other day) with heterometallic compound 5 as compared with the previously described [(η-C₅H₅)₂Ti{OC(O)-4-C₆H₄-P(Ph₂)AuCl}₂] 3 which was non-inhibitory. These findings indicate that structural modifications on the ligand scaffold affect the in vivo efficacy of this class of compounds.     

An electron donor–acceptor photoactivation strategy for the synthesis of S-aryl dithiocarbamates using thianthrenium salts under mild aqueous micellar conditions

An eco-friendly and convenient method is developed herein for the synthesis of S-aryl dithiocarbamates via visible-light-induced SET process of an EDA complex between thianthrenium salt functionalized arenes and dithiocarbamate anions under mild aqueous micellar conditions. This strategy indirectly realizes the method for constructing S-aryl dithiocarbamates through site-selective C−H functionalization of arenes. Most importantly, the reaction proceeded smoothly without addition of any photocatalyst, and the by-product thianthrene is recycled in quantity, ultimately minimizing the production of chemical waste. This protocol provides a promising synthesis candidate for the construction of valuable S-aryl dithiocarbamates, which also opens up a new avenue for micellar photocatalysis.     

Profluorescent verdazyl radicals – synthesis and characterization

The synthesis and characterization of various 6-oxo-verdazyl radicals and their diamagnetic styryl radical trapping products are presented. It is shown that styryl radical trapping products derived from N-phenyl verdazyls show fluorescence whereas the N-methyl congeners are non-fluorescent. In the parent N-phenyl verdazyls fluorescence is fully quenched which renders these compounds highly valuable profluorescent radical probes.     

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt₃, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials.     

Synthesis and photophysical properties of donor–acceptor system based bipyridylporphyrins for dye-sensitized solar cells

Bipyridylporphyrin derivatives possessing a porphyrin moiety as the electron donor and bipyridyl moiety as the electron–acceptor were designed and synthesized for dye-sensitized solar cells(DSSCs). The photophysical and electrochemical properties were investigated by absorption spectrometry and cyclic voltammetry. Density functional theory(DFT) was employed to study electron distribution. From the photovoltaic performance measurements, a maximum conversion efficiency(η) of 0.38% was achieved based on the bipyridylporphyrin ruthenium dye A7(J_(SC)= 1.33 mA/cm~2, V_(OC)= 0.45 V, FF = 0.64) under 1.5 irradiation(100 mW/cm~2).     

Structure–activity relationship studies of cyclopropenimines as enantioselective Br?nsted base catalysts

We recently demonstrated that chiral cyclopropenimines are viable Brønsted base catalysts in enantioselective Michael and Mannich reactions. Herein, we describe a series of structure–activity relationship studies that provide an enhanced understanding of the effectiveness of certain cyclopropenimines as enantioselective Brønsted base catalysts. These studies underscore the crucial importance of dicyclohexylamino substituents in mediating both reaction rate and enantioselectivity. In addition, an unusual catalyst CH···O interaction, which provides both ground state and transition state organization, is discussed. Cyclopropenimine stability studies have led to the identification of new catalysts with greatly improved stability. Finally, additional demonstrations of substrate scope and current limitations are provided herein.     

Well-defined silica supported aluminum hydride: another step towards the utopian single site dream?

Reaction of triisobutylaluminum with SBA15₇₀₀ at room temperature occurs by two parallel pathways involving either silanol or siloxane bridges. It leads to the formation of a well-defined bipodal [(SiO)₂Al–CH₂CH(CH₃)₂] 1a, silicon isobutyl [Si–CH₂CH(CH₃)₂] 1b and a silicon hydride [Si–H] 1c. Their structural identity was characterized by FT-IR and advanced solid-state NMR spectroscopies (¹H, ¹³C, ²⁹Si, ²⁷Al and 2D multiple quantum), elemental and gas phase analysis, and DFT calculations. The reaction involves the formation of a highly reactive monopodal intermediate: [SiO–Al–[CH₂CH(CH₃)₂]₂], with evolution of isobutane. This intermediate undergoes two parallel routes: transfer of either one isobutyl fragment or of one hydride to an adjacent silicon atom. Both processes occur by opening of a strained siloxane bridge, Si–O–Si but with two different mechanisms, showing that the reality of “single site” catalyst may be an utopia: DFT calculations indicate that isobutyl transfer occurs via a simple metathesis between the Al-isobutyl and O–Si bonds, while hydride transfer occurs via a two steps mechanism, the first one is a β-H elimination to Al with elimination of isobutene, whereas the second is a metathesis step between the formed Al–H bond and a O–Si bond. Thermal treatment of 1a (at 250 °C) under high vacuum (10^–5 mbar) generates Al–H through a β-H elimination of isobutyl fragment. These supported well-defined Al–H which are highly stable with time, are tetra, penta and octa coordinated as demonstrated by IR and ²⁷Al–¹H J-HMQC NMR spectroscopy. All these observations indicate that surfaces atoms around the site of grafting play a considerable role in the reactivity of a single site system.