Solid-State Near-Infrared Circularly Polarized Luminescence from Chiral YbIII-Single-Molecule Magnet

A field-induced chiral Yb^III Single-Molecule Magnet (SMM) displayed an unprecedented near-infrared circularly polarized luminescence (NIR-CPL) in the solid-state. The bridging bis(1,10-phenantro[5,6b])tetrathiafulvalene triad ( L ) allowed an efficient sensitization of the NIR ²F_5/2→²F_7/2 emission while the NIR-CPL is associated to the f-f transitions of the Yb^III ion bearing chiral β-diketonate derived-camphorate ancillary ligands.     

Near-Infrared Circularly Polarized Luminescence through Intramolecular Excimer Formation of Oligo(p-phenyleneethynylene)-Based Double Helicates

Carbon-based double helicates consisting of two anthracene-containing oligo(p-phenyleneethynylene) units and two flexible chiral 1,1′-binaphthyl units or two rigid chiral 9,9′-spirobifluorene units were developed. The curved oligo(p-phenyleneethynylene) fragments in the double helicates were successfully constructed by tin-mediated reductive aromatization. Helical oligo(p-phenyleneethynylene) double strands fixed by two rigid spirobifluorene units showed little structural change under photoirradiation, thereby emitting circularly polarized luminescence (CPL) in the visible region with a high quantum yield (Φ_PL=0.93). In contrast, flexible binaphthyl units induced dynamic structural change of the oligo(p-phenyleneethynylene) luminophores under photoirradiation, leading to strong CPL (|g_lum|=1.1×10⁻²) in the near-infrared (NIR) region. UV/Vis, circular dichroism (CD), CPL and NMR spectroscopic analyses of the binaphthyl-hinged double helicate suggested excimer formation between two π-conjugated strands in the excited state. Theoretical calculations highlight the importance of the tightly interlocked excimer structure of the carbon-based double helicate in controlling the angle between the electric and magnetic transition dipole moments for strong NIR CPL generation.     

Chiral Sensing of Various Amino Acids Using Induced Circularly Polarized Luminescence from Europium(III) Complexes of Phenanthroline Dicarboxylic Acid Derivatives

Circularly polarized luminescence (CPL) was observed from [Eu(dppda)₂]^? (dppda=4,7‐diphenyl‐1,10‐phenanthroline‐2,9‐dicarboxylic acid) and [Eu(pzpda)₂]^? (pzpda=pyrazino[2,3‐f][1,10]phenanthroline‐7,10‐dicarboxylic acid) in aqueous solutions containing various amino acids. The selectivity of these complexes towards amino acids enabled them to be used as chiral sensors and their behavior was compared with that of [Eu(pda)₂]^? (pda=1,10‐phenanthroline‐2,9‐dicarboxylic acid). As these Eu^III complexes have achiral D_2d structures under ordinary conditions, there were no CPL signals in the emission assigned to f–f transitions. However, when the solutions contained particular amino acids they exhibited detectable CPL signals with g_lum values of about 0.1 (g_lum=CPL/2 TL; TL=total luminescence). On examining 13 amino acids with these three Eu^III complexes, it was found that whether an amino acid induced a detectable CPL depended on the Eu^III complex ligands. For example, when ornithine was used as a chiral agent, only [Eu(dppda)₂]^? exhibited intense CPL in aqueous solutions of 10^?2 mol dm^?3. Steep amino acid concentration dependence suggested that CPL in [Eu(dppda)₂]^? and [Eu(pzpda)₂]^? was induced by the association of four or more amino acid molecules, whereas CPL in [Eu(pda)₂]^? was induced by association of two arginine molecules.     

Synthesis and Chiroptical Properties of Chiral Carbazole-Based BODIPYs

A series of carbazole-based boron dipyrromethenes (BODIPYs) 2 a – g bearing binaphthyl units have been synthesized by the Et₂AlCl-mediated reaction of the corresponding BODIPY difluorides 1 a – g with 1,1′-binaphthalene-2,2′-diol. Substituents such as halogen, nitrile, and amino groups were tolerated under the reaction conditions, and the reaction of the phenylethynyl-substituted 1 h gave (R,R)- 3 h bearing two binaphthyl units. The chiroptical properties of these dyes with different substituents were investigated by UV/Vis, CD, fluorescence, and circularly polarized luminescence (CPL) spectroscopy. The CD spectra showed Cotton effects in the absorption region of the BODIPY moieties. In addition, they showed CPL both in solution and in the solid state. Interestingly, several dyes recorded higher g_lum values in the solid state, probably due to intermolecular interactions. Because (R,R)- 3 h recorded relatively low g_lum values, the diastereomer (R,S)- 3 h was prepared. The (R,S) diastereomer showed intense CPL, which suggests a synergetic effect of the two binaphthyl groups. Finally, chiral carbazole-based BODIPY dimers have been synthesized for the first time and their chiroptical properties were investigated. They showed redshifted fluorescence and CPL, which reached the near-IR (NIR) region in the solid state.     

Amino-Acid-Induced Circular Polarized Luminescence in One-Dimensional Manganese(II) Halide Hybrid

Circular polarized luminescence (CPL)-active materials attract great attentions owing to their widely applications in 3D optical displays and encrypted transmission. Inspired by the strategies adopted in perovskite based CPL materials, herein, CPL-active hybrids (D)- and (L)-(tert-butyl prolinate)MnCl₃ were successfully prepared by assembling chiral D/L tert-butyl prolinate with manganese (II) chloride. Single crystal structures show the as-formed hybrids possess one-dimensional (1D) structure containing linear chains of face-sharing MnCl₆ octahedral surrounded by prolinate cations. The 1D Mn(II) hybrids display strong red emission peaked at 646 nm with PLQY of 67.1 % and 57.2 % for d -type and l -type, respectively, representing the highest PLQY for 1D Mn^II hybrids. Interestingly, the 1D Mn(II) hybrids exhibit prominent circular dichroism (CD) signals and remarkable CPL activity with the dissymmetry factor g of 6.1*10⁻³ and −6.3*10⁻³ from 550 to 800 nm for (D)- and (L)-(tert-butyl prolinate)MnCl₃, respectively, owing to the existence of chiral cations. It is worthy noted the obtained g represents the highest value for non-lead organic–inorganic hybrids.     

长波敏化发光铕配合物纳米粒子的制备与表征

以牛血清白蛋白(BSA)为保护剂, 利用沉淀法制备了平均粒径为35 nm的Eu(tta)3dpbt (dpbt = 2-(N,N-二乙基苯胺-4-基)-4,6-二(3,5-二甲基吡唑-1-基)-1,3,5-三嗪, tta = 噻吩甲酰三氟丙酮负离子)荧光纳米粒子. BSA保护Eu(tta)3dpbt纳米粒子在水中分散稳定性高, 光稳定性好, 长波敏化发光性能优良. 其在可见光区激发峰位于415 nm, 激发峰尾部延展至470 nm, 发光量子产率为0.20 (λex=415 nm, 25 ℃). 在近红外双光子激发下可发出纯正的红光, Eu(tta)3dpbt纳米粒子最大双光子激发作用截面为2.4×10⁵ GM (λex=830 nm, 1 GM=10^-50 cm⁴·s·photo^-1·particle^-1).     

Multifunctional Helicene-Based Ytterbium Coordination Polymer Displaying Circularly Polarized Luminescence,Slow Magnetic Relaxation and Room Temperature Magneto-Chiral Dichroism**

The combination of physical properties sensitive to molecular chirality in a single system allows the observation of fascinating phenomena such as magneto-chiral dichroism (MChD) and circularly polarized luminescence (CPL) having potential applications for optical data readout and display technology. Homochiral monodimensional coordination polymers of Yb^III were designed from a 2,15-bis-ethynyl-hexahelicenic scaffold decorated with two terminal 4-pyridyl units. Thanks to the coordination of the chiral organic chromophore to Yb(hfac)₃ units (hfac⁻=1,1,1,5,5,5-hexafluoroacetylaconate), efficient NIR-CPL activity is observed. Moreover, the specific crystal field around the Yb^III induces a strong magnetic anisotropy which leads to a single-molecule magnet (SMM) behaviour and a remarkable room temperature MChD. The MChD-structural correlation is supported by computational investigations.     

Rhodium-Catalyzed Enantioselective Synthesis of Highly Fluorescent and CPL-Active Dispiroindeno[2,1-c]fluorenes

The enantioselective synthesis of chiral [7]-helical dispirodihydro[2,1-c]indenofluorenes (DSF-IFs) was achieved for the first time in good yields with high er values (er up to 99 : 1). The crucial step of the whole reaction sequence was the enantioselective intramolecular [2+2+2] cycloaddition of tethered triynediols to indenofluorenediols, which was catalyzed by a Rh/SEGPHOS® complex. Further transformations led to the corresponding DSF-IFs. The prepared helically chiral DSF-IFs combine circularly polarized luminescence (CPL) activity (g_lum=∼10⁻³) with exceptionally high fluorescence quantum yields (up to Φ_lum=0.97).     

Chiral Sensing Using Circularly Polarized Luminescence of Bis(phenanthroline dicarboxylic acid) EuIII Complex Induced by Allosteric‐type Interaction with Amino Acid Molecules

[Eu(pda)₂]^? and [Eu(bda)₂]^? (pda=1,10‐phenanthroline‐2, 9‐dicarboxylic acid; bda=2,2′ bipyridine 5,5′‐dicarboxylic acid) have an achiral D_2d structure in crystals. These complexes exhibit circularly polarized luminescence (CPL) in water containing chiral amino acids. In this work, induced CPL of [Eu(pda)₂]^? and [Eu(bda)₂]^? in water solutions containing a mixture of d ‐ and l ‐ amino acids were examined. Plots of g_lum values of the induced CPL as a function of mol‐fraction of l ‐ and d ‐ arginine reveal that [Eu(pda)₂]^? favors homo‐association ([Eu(pda)₂]^?‐(l ‐arginine)₂ or [Eu(pda)₂]^?‐(d ‐arginine)₂) over hetero‐association {[Eu(pda)₂]^?‐(l ‐arginine)?(d ‐arginine)}. This suggests that association of an arginine molecule induces a structural change in [Eu(pda)₂]^? to promote chiral selective association to another arginine, i.e., homo‐allosteric association. On the other hand, the system of [Eu(pda)₂]^? with histidine favors hetero‐allosteric association over homo‐association. No allosteric effect is recognized in CPL from [Eu(bda)₂]^?.     

Ring-Opened Hemiporphyrazines: Helical Molecules Exhibiting Circularly Polarized Luminescence

We designed and synthesized a new type of small helical molecule exhibiting intense circularly polarized luminescence (CPL) ( 1_2H ) by modifying a 20π-electron hemiporphyrazine with a large transition magnetic dipole moment. The hemiporphyrazine ring was opened and one additional pyridine unit was introduced, resulting in an overlap of two pyridine rings. X-ray structure analysis confirmed that 1_2H and its zinc complex ( 1_Zn ) adopt a helical geometry. A racemic mixture of 1_Zn was resolved into two enantiomers ((P)- and (M)- 1_Zn ), which exhibited CPL with a high luminescence dissymmetry factor (g_lum) value of ±2.1×10⁻². The origin of the large g_lum value was rationalized by means of DFT calculations. Helical structures could be formed in a diastereoselective manner by covalently attaching chiral units to the skeleton ( 1’_2H and 1’_Zn ). 1_Zn was found to possess chiral recognition ability for amines.     

Yellow Circularly Polarized Luminescence from C1‐Symmetrical Copper(I) Complexes

The synthesis of chiral C₁‐symmetrical copper(I) complexes supported by chiral carbene ligands is described. These complexes are yellow emitters with modest quantum yields. Circularly polarized luminescence (CPL) spectra show a polarized emission band with dissymmetry factors |g_lum|=1.2×10^?3. These complexes are the first reported examples of molecular copper(I) complexes exhibiting circularly polarized luminescence. In contrast with most CPL‐emitting molecules, which possess either helical or axial chirality, the results presented show that simple chiral architectures are suitable for CPL emission and unlock new synthetic possibilities.     

2D l‐Di‐toluoyl‐tartaric acid Lanthanide Coordination Polymers: Toward Single‐component White‐Light and NIR Luminescent Materials

A series of five l ‐di‐p‐toluoyl‐tartaric acid (l ‐DTTA) lanthanide coordination polymers, namely {[Ln₄K⁴ L₆(H₂O)_x]?yH₂O}_n, [Ln=Dy ( 1 ), x=24, y=12; Ln=Ho ( 2 ), x=23, y=12; Ln=Er ( 3 ), x=24, y=12; Ln=Yb ( 4 ), x=24, y=11; Ln=Lu ( 5 ), x=24, y=12] have been isolated by simple reactions of H₂L (H₂L= L ‐DTTA) with LnCl₃?6 H₂O at ambient temperature. X‐ray crystallographic analysis reveals that complexes 1 – 5 feature two‐dimensional (2D) network structures in which the Ln³⁺ ions are bridged by carboxylate groups of ligands in two unique coordinated modes. Luminescent spectra demonstrate that complex 1 realizes single‐component white‐light emission, while complexes 2 – 4 exhibit a characteristic near‐infrared (NIR) luminescence in the solid state at room temperature.     

Luminescent Chiral Exciplexes with Sky-Blue and Green Circularly Polarized-Thermally Activated Delayed Fluorescence

Luminescent exciplexes based on a chiral electron donor and achiral acceptors are reported as a new approach to design circularly polarized (CP) and thermally activated delayed fluorescence (TADF) emitters. This strategy results in rather high CP luminescence (CPL) values with g_lum up to 7×10⁻³, one order of magnitude higher in comparison to the CPL signal recorded for the chiral donor alone (g_lum ∼7×10⁻⁴). This increase occurs concomitantly with a CPL sign inversion, as a result of the strong charge-transfer emission character, as experimentally and theoretically rationalized by using a covalent chiral donor-acceptor model. Interestingly, blue, green-yellow and red chiral luminescent exciplexes can be obtained by modifying with the electron accepting character of the achiral unit while keeping the same chiral donor unit. These results bring new (inter)molecular guidelines to obtain simply and efficiently multi-color CP-TADF emitters.     

Microscopic Imaging of Chiral Amino Acids in Agar Gel through Circularly Polarized Luminescence of EuIII Complex

We recently found that [Eu(pda)₂]^? (pda: 1,10‐phenanthroline‐2,9‐dicarboxylic acid), which has an achiral structure in crystals, exhibits circularly polarized luminescence (CPL) in aqueous solutions containing chiral amino acids such as arginine and histidine. CPL measurements were performed for agar gel, which includes an aqueous solution of [Eu(pda)₂]^? and chiral arginine or histidine. The spectral shape, concentration, and pH dependences on CPL intensity in the agar gels were very close to those in aqueous solutions, indicating that the CPL of the Eu^III complex in the agar gels was induced by mechanism similar to that in aqueous solutions. We performed spatially resolved CPL measurements using a laboratory‐built microscopic CPL spectroscopic system for agar‐gel samples, where d ‐ and l ‐ amino acids were separately dispersed. We successfully recorded CPL imaging maps showing spatial dispersions of d ‐ and l ‐amino acid in the agar gels.     

Helically Assembled Pyrene Arrays on an RNA Duplex That Exhibit Circularly Polarized Luminescence with Excimer Formation

Circularly polarized luminescence (CPL) was observed in pyrene zipper arrays helically arranged on an RNA duplex. Hybridization of complementary RNA strands having multiple (two to five) 2′‐O‐pyrenylmethyl modified nucleosides affords an RNA duplex with normal thermal stability. The pyrene fluorophores are assembled like a zipper in a well‐defined helical manner along the axis of RNA duplex, which, upon 350 nm UV illumination, resulted in CPL emission with pyrene excimer formation. CPL (g_lum) levels observed for the pyrene arrays in dilute aqueous solution were +2×10^?2–+3.5×10^?2, which are comparable with |g_lum| for chiral organic molecules and related systems. The positive CPL signals are consistent with a right‐handed helical structure. Temperature dependence on CPL emission indicates that the stable rigid RNA structure is responsible for the strong CPL signals. The single pyrene‐modified RNA duplex did not show any CPL signal.     

The preparation and performance of visible-light-sensitized luminescent nanoparticles based on europium complex

Long-wavelength-sensitized luminescent materials are desired for bio-detection. In this paper, we prepared a new kind of luminescent europium nanoparticles by a co-precipitation-condensation method. The luminescent europium complex Eu（tta）3.bpt （tta = thenoyltrifluoroacetonate; bpt = 2-（N,N- di-ethylanilin-4-yl）-4,6-bis（pyrazol-l-yl）-l,3,5-triazine） was used as the active material, being encapsulated in the nanoparticles formed from 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane （PFOTS） and poly（styrene-co-methyl methacrylate） [P（ST-co-MMA）]. The prepared nanoparticles not only can be well dispersed in water but also were of high photostability. Importantly, the nanoparticles displayed maximal excitation wavelength at 425 nm as well as an extended excitation wavelength up to 480 nm and a quantum yield for Eu3＋ luminescence of 0.22 （λex= 425 nm, room temperature）.     

Discriminating Chiral Supramolecular Motions by Circularly Polarized Luminescence

Molecular motions are closely associated with the behaviors and properties of organic materials. However, monitoring molecular motions is challenging. Herein, a chiral supramolecular system consisting of L-/D-phenylalanine (LPF/DPF) as a chiral inducer and an achiral tetraphenylethene derivative (TPEF) as a molecular rotor has been proposed and explored for real-time discriminating the supramolecular motions by the visualization of circularly polarized luminescence (CPL) signal variations. Derived from the ordered molecular motions of TPEF induced by LPF/DPF, highly organized aggregates have been progressively assembled in a controlled manner with differentiated morphologies, including spherical particles, one-dimensional fibers, and floor-shaped supercrystals. Notably, increasing level of ordered aggregates, in turn, led to quenching emissions, while the CPL signals have been dramatically amplified accompanying by a sharp enhancement of luminescence dissymmetry factors (g_lum) from nearly 0 to −0.1. The significant amplification of CPL is attributed to the ordered aggregates of supramolecules, leading to the decrease of electric transition dipole moments in supramolecular system. As a result of the chiral supramolecular motions powered by supramolecular crystallization, the supramolecular motions are conveniently discriminated by visual CPL signal variation with an enhancement of g_lum value from 0 to −0.1 in real time.     

Enhanced Circularly Polarized Luminescence from Reorganized Chiral Emitters on the Skeleton of a Zeolitic Imidazolate Framework

A chiral zeolitic imidazolate framework (ZIF) showing circularly polarized luminescence (CPL) has been successfully constructed by blending binapthyl‐derived chiral emitters with ZIF‐8 rhombic dodecahedron nanoparticles. This approach solves a major trade‐off in CPL‐active materials: the large luminescence dissymmetry factor (g_lum) always suffers from suppression of luminescence efficiency. Compared to the optical properties of chiral emitters, the obtained chiral ZIF nanomaterials showed an enhanced fluorescence efficiency while the |g_lum| value is significantly amplified by one order of magnitude. Additionally, enantioselective fluorescence sensing in response to α‐hydroxycarboxylic acids has been enhanced in chiral ZIFs. Reorganization and conjunction of chiral emitters to the skeleton of ZIF nanoparticles can greatly improve both the luminescence quantum yield and circularly polarization, which facilitates the design of more efficient chiroptical materials.     

New Types of Planar Chiral [2.2]Paracyclophanes and Construction of One‐Handed Double Helices

New types of planar chiral (R_p)‐ and (S_p)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes were synthesized from racemic 4,12‐dihydroxy[2.2]paracyclophane as the starting compound. Regioselective dibromination and transformation afforded a series of planar chiral (R_p)‐ and (S_p)‐4,7,12,15‐tetrasubstituted [2.2]paracyclophanes, which can be used as chiral building blocks. In this study, left‐ and right‐handed double helical structures were constructed via chemoselective Sonogashira–Hagihara coupling. The double helical compounds were excellent circularly polarized luminescence (CPL) emitters with large molar extinction coefficients, good photoluminescence quantum efficiencies, and large CPL dissymmetry factors.     

NIR-Circularly Polarized Luminescence from Chiral Complexes of Lanthanides and d-Metals

In recent years, circularly polarized luminescence (CPL) has witnessed a renaissance, due to the increased popularity of CPL as a spectroscopic technique and greater accessibility to instrumentation. New efficient CPL emitters have been designed and many applications, ranging from electronic devices to microscopy have been proposed. Most examples of CPL are within the visible range, while few cases of near infrared (NIR) CPL active complexes are available. NIR-CPL compounds may have applications in the telecommunication industry, electronic devices and bioassays. In the following, we shall give an overview of the recent developments allowing for the measurements of NIR-CPL, and describe the chiroptical properties of metal complexes which achieve this feat.