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This study explores peptide-mediated chiral induction and circularly polarized luminescence (CPL) in achiral BODIPY dyes, leading to a high glum value of up to −1.2 × 10−2 through orthogonal halogen bonding and hydrogen bonding. It unravels the impact of these combined directional interactions on the formation of heterostructures and their thermal stability. [ABSTRACT FROM AUTHOR]

Upconverted circularly polarized luminescence (UC‐CPL) which is coined by integrating two concepts of photon upconversion and circularly polarized luminescence, has aroused enormous attention from scientists owing to the great performance and potential applications in various fields. To date, although various types of UC‐CPL systems are reported, constructing a UC‐CPL system with multicolor emission remains a big challenge. In this work, by incorporating lanthanide‐doped upconversion nanoparticles (UCNPs) into chiral nematic liquid crystal (N*LC), multicolor UC‐CPL emission can be realized upon two kinds of modulations: the regulation of photonic bandgap (PBG) and adjustment of excitation wavelength of the doped UCNPs. More importantly, this kind of multicolor UC‐CPL system can be used as internal materials for constructing polymer‐shell microcapsules. The PBG effect can still be well preserved in the microcapsules, providing a kind of easy processable luminescent material with multicolor UC‐CPL properties, which can be used as an advanced anti‐counterfeiting material. [ABSTRACT FROM AUTHOR]

Functional materials with circularly polarized luminescence (CPL) have attracted tremendous attention due to their promising applications in three-dimensional displays, chiral recognition and catalysis, photoelectronic devices, contrast imaging, information encryption, and other fields. Among various CPL-active materials, polymeric systems with aggregation-induced emission (AIE) have emerged as excellent candidates because of their efficient aggregate-state fluorescence, large solid-state dissymmetry factor, excellent processibility, diversified self-assembly behaviors, and readily switchable CPL properties. This review summarizes and discusses the recent progress as well as future perspective of diverse AIE polymer systems with CPL, including CPL-active covalent AIE polymers, CPL-active supramolecular AIE polymers, and AIEgen/polymer composites with CPL. According to the location or introduction method of AIEgen in polymer structures, this review further divides CPL-active covalent AIE polymers into three categories, including polymers with AIEgen in main chains, polymers with AIEgen in side chains, and CPLactive polymers with clusterization-triggered emission. CPL-active supramolecular AIE polymers are discussed based on the driving force for the formation of supramolecular polymers, including host-guest interactions, metal coordination, and other non-covalent interactions. Moreover, examples on the construction of CPL-active AIEgen/polymer composites by physically mixing AIEgens with chiral (supra)polymers are also presented. This review is anticipated to provide readers with an overall view on the design strategies of CPL-active AIE polymers, and facilitate further research on the development of CPL materials and AIE polymers with advanced applications. [ABSTRACT FROM AUTHOR]

A new pair of multifunctional Zn(II)–Dy(III) enantiomers based on the chiral Schiff-base ligands [R,R-ZnLDy(H2O)(NO3)3] (1R2R-ZnDy) and [S,S-ZnLDy(H2O)(NO3)3] (1S2S-ZnDy) (H2L = phenol, 2,2′-[[(1R,2R/1S,2S)-1,2-diphenyl-1,2-ethanediyl]bis[(E)-nitrilomethylidyne]]bis[6-methoxy]) was synthesized and characterized. Magnetic studies indicate that 1R2R-ZnDy behaves as a single-molecule magnet. Enantiomers 1R2R-ZnDy and 1S2S-ZnDy show chiroptical activity and circularly polarized luminescence in the N,N-dimethylformamide (DMF) solution. The chiral Zn(II)–Dy(III) complexes display magnetic circular dichroism signals at room temperature. Accordingly, these complexes will inspire intriguing research on single-molecule magnets with circular polarization of luminescence activity and magneto-optic effects, which will give new clues to design multifunctional molecular magnetic materials. [ABSTRACT FROM AUTHOR]

The development of circularly polarized electroluminescence (CPEL) is currently hampered by the high difficulty and cost in the syntheses of suitable chiral materials and the notorious chirality diminishment issue in electrical devices. Herein, diastereomeric IrIII and RuII complexes with chiral (±)‐camphorsulfonate counteranions are readily synthesized and used as the active materials in circularly polarized light‐emitting electrochemical cells to generate promising CPELs. The addition of the chiral ionic liquid (±)‐1‐butyl‐3‐methylimidazole camphorsulfonate into the active layer significantly improves the device performance and the electroluminescence dissymmetry factors (≈10−3), in stark contrast to the very weak circularly polarized photoluminescence of the spin‐coated films of these diastereomeric complexes. Control experiments with enantiopure IrIII complexes suggest that the chiral anions play a dominant role in the electrically‐induced amplification of CPELs. [ABSTRACT FROM AUTHOR]

The development of circularly polarized electroluminescence (CPEL) is currently hampered by the high difficulty and cost in the syntheses of suitable chiral materials and the notorious chirality diminishment issue in electrical devices. Herein, diastereomeric IrIII and RuII complexes with chiral (±)‐camphorsulfonate counteranions are readily synthesized and used as the active materials in circularly polarized light‐emitting electrochemical cells to generate promising CPELs. The addition of the chiral ionic liquid (±)‐1‐butyl‐3‐methylimidazole camphorsulfonate into the active layer significantly improves the device performance and the electroluminescence dissymmetry factors (≈10−3), in stark contrast to the very weak circularly polarized photoluminescence of the spin‐coated films of these diastereomeric complexes. Control experiments with enantiopure IrIII complexes suggest that the chiral anions play a dominant role in the electrically‐induced amplification of CPELs. [ABSTRACT FROM AUTHOR]

We found that the complexes of nucleotides and terbium(III) exhibit circularly polarized luminescence (CPL). The CPL of GMP/Tb/Ag coordination polymer nanoparticles (CPNs) was converted by a magnetic field and pH. The CPL of the purine nucleobase of nucleotides was opposite to that of the pyrimidine nucleobase. GMP/Tb/Ag CPNs could be used as advanced safety coatings and acid–base switches, and Tb/Ag could be used as CPL probes for rapid differentiation of nucleotides, which provided ideas for multiple transformations and applications of CPL. [ABSTRACT FROM AUTHOR]

Due to their numerous potential applications, the interest for the elaboration of new molecular switch has never stop to grow. Among them, multi‐modal systems, where the switching between two different metastable states can be induced by using indifferently several kinds of stimulation, have a special place. In this study, we present our efforts to develop a class of multi‐modal systems based on the association of a triphenylamine core with vinylpyrimidine units that exhibits nice acido and electrochromic properties. The most performant ones can present up to three different forms allowing to modulate their absorption and luminescence properties over three discrete levels. In order to provide limitations and outlooks for such systems, their switching behaviors have been rationalized by the help of DFT and TD‐DFT calculations. [ABSTRACT FROM AUTHOR]

Three types of Eu(III) coordination polymers with different distorted chiral ligands, [Eu(+tfc)3(p-dpeb)]n, [Eu(+pfc)3(p-dpeb)]n, and [Eu(+hfc)3(p-dpeb)]n (+tfc: (+)-3-(trifluoroacetyl)camphorate, +pfc: (+)-3-(pentafluoropropionyl)camphorate, +hfc: (+)-3-(heptafluorobutyryl)camphorate, p-dpeb: 1,4-bis(diphenylphosphorylethynyl)benzene), were prepared for elucidating the relationship between their structural distortions, ligand-to-metal charge transfer (LMCT), and circularly polarized luminescence (CPL) properties. Their strain factors in the ligands were evaluated using crystallographic data obtained by single-crystal X-ray structural analyses. The characteristics of the LMCT excited states were estimated from theoretical calculations. The introduction of a bulky substituent into the chiral ligand afforded a distorted structure of β-diketonates and changed the direction of the transition electric dipole moments, which are related to the magnitude of the CPL intensity. The CPL dissymmetry factor (gCPL) of [Eu(+hfc)3(p-dpeb)]n, with a large distorted structure, was −0.22, while those of [Eu(+tfc)3(p-dpeb)]n and [Eu(+pfc)3(p-dpeb)]n, with small distorted structures, were −0.05 and −0.10, respectively. The controlled steric hindrance of the chiral ligands in Eu(III) coordination polymers is one of the strain factors enhancing their CPL properties. [ABSTRACT FROM AUTHOR]

A molecular cage-based approach to obtain enantiopure lanthanide complexes with circular polarized luminescence (CPL) activities is presented. Hemicryptophane endohedral complexes were designed by functionalizing the molecular cage with pyridine-2,6-dipicolinamide coordinating groups. Taking advantage of the ability of the inherent chirality of the remote cyclotriveratrylene (CTV) unit to propagate along the linkers of the molecular cage, the encapsulated lanthanide complexes with a controlled chirality have been obtained. In this way, we obtained the CPL active Tb(III) and Eu(III) cages although the chiral CTV unit is located far from the complexation sites. This opens the way for a broader use of enantiopure covalent cages for CPL applications. [ABSTRACT FROM AUTHOR]

Herein, we report the structures of chiral‐at‐cage carborane derivatives bearing carbazole chromophores that emit circularly polarized luminescence (CPL) and aggregation‐induced electrochemiluminescence (AIECL). By adjusting the substituent positions on the carborane derivatives, two chiral luminescent molecules, Cb1 and Cb2, with different properties were obtained. The photoluminescence dissymmetry factors |gPL| of both (R/S)‐Cb1 and (R/S)‐Cb2 enantiomers in neat films were as high as 6.24×10−3 and 7.38×10−3, respectively. Cb1 showed a deep blue emission peak at 434 nm in n‐pentane. Interestingly, distinct fluorescence and CPL spectra were observed in solvents of different polarities due to the twisted intramolecular charge transfer effect, suggesting its potential use in solvent recognition. Meanwhile, Cb2 exhibited good AIECL property, excellent ECL stability and could be used for determining dopamine concentrations, suggesting its potential applications in biology and diagnosis. [ABSTRACT FROM AUTHOR]

Herein, we report the structures of chiral‐at‐cage carborane derivatives bearing carbazole chromophores that emit circularly polarized luminescence (CPL) and aggregation‐induced electrochemiluminescence (AIECL). By adjusting the substituent positions on the carborane derivatives, two chiral luminescent molecules, Cb1 and Cb2, with different properties were obtained. The photoluminescence dissymmetry factors |gPL| of both (R/S)‐Cb1 and (R/S)‐Cb2 enantiomers in neat films were as high as 6.24×10−3 and 7.38×10−3, respectively. Cb1 showed a deep blue emission peak at 434 nm in n‐pentane. Interestingly, distinct fluorescence and CPL spectra were observed in solvents of different polarities due to the twisted intramolecular charge transfer effect, suggesting its potential use in solvent recognition. Meanwhile, Cb2 exhibited good AIECL property, excellent ECL stability and could be used for determining dopamine concentrations, suggesting its potential applications in biology and diagnosis. [ABSTRACT FROM AUTHOR]

This work reports the development of external magnetic field (EMF) driven, ambidextrous, circularly polarized electroluminescence (CPEL) devices, by embedding racemic mixtures of phosphorescent organoiridium(III) emitters in the active emitting layer. Homoleptic tris‐cyclometalated Ir(III)(ppy)3 and heteroleptic bis‐cyclometalated Ir(III)(ppy)2(acac) (ppy=2‐phenylpyridinate, acac=acetylacetonate) were used as the representative organoiridium(III) compounds. Chiroptical inversion of CPEL was influenced by the ligand environment in the Ir(III) complexes (homoleptic or heteroleptic), as well as the Faraday geometry. [ABSTRACT FROM AUTHOR]

Circular polarization of luminescence is a phenomenon that can be observed for chiral molecules in isotropic solution, for molecular aggregates and molecular materials. Also, the electroluminescence from chiral molecular materials in organic light emitting diodes can be nearly completely circularly polarized. In this review we focus on the latest developments in experimental results for the categories listed above. A unifying description of the origin of the circular polarization is still missing. We revisit the very earliest efforts to measure and understand circular polarization in light emission in order to better understand the present day confusion on the origins of the polarization. It seems that quantum field theory of electromagnetic interactions could provide leads for a comprehensive description of the circular polarization including contributions from helicity at all possible length scales from the molecular to the macroscopic. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DES) or eutectic mixtures prepared with a chiral component can lead to new chiral solvents with applications that include asymmetric synthesis and chiral light emitting materials. DES have low melting points, because of strong interactions, such as hydrogen bonding, between components of the mixture. Mixtures are prepared with ammonium salts, tetrabutylammonium chloride ([TBA]Cl) and choline chloride ([Ch]Cl), as hydrogen bond acceptor (HBA) and L‐lactic acid, L‐leucic acid, L‐ascorbic acid, R/S‐acetoxypropionic acid, and methyl‐(S)‐lactate as chiral hydrogen bond donors (HBD). Eight combinations of the HBAs and HBDs were prepared, and a racemic mixture of dissymmetric chiral europium complexes was dissolved in the mixtures. The circularly polarized luminescence (CPL) spectra were measured to determine the chiral discrimination by these chiral solvents. The CPL spectra show that the handedness of the chiral HBD is important to the chiral discrimination exhibited. However, the inversion of the sign of the CPL spectra in 1 : 3 [TBA]Cl:L‐lactic acid vs. 1 : 3 [Ch]Cl:L‐lactic acid, and 1 : 1.5 [Ch]Cl:L‐leucic acid vs. 1 : 1 [TBA]Cl:L‐leucic acid shows that the achiral HBA also plays a critical role in the handedness of the chiral discrimination by the chiral solvent. [ABSTRACT FROM AUTHOR]

A series of chiral platina[5]helicenes displaying dual luminescence, i.e., fluorescence between 450 and 600 nm and red/NIR phosphorescence between 700 and 900 nm, has been synthesised, characterised and studied by first-principle calculations. This unusual behavior has been attributed to limited electronic interactions between the d orbitals of the metal and the π-orbitals of the organic ligand on the excited-state. Accordingly, the electron richness of the donor group on the helical ligand does not affect the energy of the phosphorescence process but does play a role on its efficiency. Interestingly, near-infrared circularly polarized luminescence can be obtained for the three complexes with dissymmetry factors up to 3 × 10−3 at 750 nm. [ABSTRACT FROM AUTHOR]

Self‐assembled chiroptical materials have attracted considerable attention due to their great applications in wide fields. During the chiral self‐assembly, it remains unknown how achiral molecules can affect the assembly process and their final chiroptical performance. Herein, we report an achiral molecule directed chiral self‐assembly via halogen bonds, exhibiting not only an unprecedented chiral fractal architecture but also significantly amplified circularly polarized luminescence (CPL). Two axially chiral emitters with halogen bond sites co‐assemble with an achiral 1,4‐diiodotetrafluorobenzene (F4DIB) and well‐ordered chiral fractal structures with asymmetry amplification are obtained. The enhancement of the dissymmetry factors of the assemblies was up to 0.051 and 0.011, which was approximately 100 folds than those of the corresponding molecules. It was found that both the design of the chiral emitter and the highly directional halogen bond played an important role in hierarchically chirality transfer from chiral emitters to the micrometer scale chiral fractal morphology and amplified dissymmetry factors. We hope that this strategy can give a further insight into the fabrication of structurally unique featured highly efficient chiroptical materials. [ABSTRACT FROM AUTHOR]

Self‐assembled chiroptical materials have attracted considerable attention due to their great applications in wide fields. During the chiral self‐assembly, it remains unknown how achiral molecules can affect the assembly process and their final chiroptical performance. Herein, we report an achiral molecule directed chiral self‐assembly via halogen bonds, exhibiting not only an unprecedented chiral fractal architecture but also significantly amplified circularly polarized luminescence (CPL). Two axially chiral emitters with halogen bond sites co‐assemble with an achiral 1,4‐diiodotetrafluorobenzene (F4DIB) and well‐ordered chiral fractal structures with asymmetry amplification are obtained. The enhancement of the dissymmetry factors of the assemblies was up to 0.051 and 0.011, which was approximately 100 folds than those of the corresponding molecules. It was found that both the design of the chiral emitter and the highly directional halogen bond played an important role in hierarchically chirality transfer from chiral emitters to the micrometer scale chiral fractal morphology and amplified dissymmetry factors. We hope that this strategy can give a further insight into the fabrication of structurally unique featured highly efficient chiroptical materials. [ABSTRACT FROM AUTHOR]

The search for chiral chromophores with efficient circularly polarized luminescence (CPL) is an on‐going hot topic in chemistry due to their potential applications in emerging fields such as spintronics and photonics. Beyond the largely exploited p‐block, 4d/5d‐block and f‐block chiral entities, chiral chromium(III) complexes have recently attracted interest because of the abundancy of chromium in the earth's crust, its kinetic inertness and its promising metal‐centered Cr(2E) and Cr(2T1) phosphorescence. The associated spin‐flip transitions could provide large dissymmetric factor (glum) and high luminescence quantum yields (ϕ) when six‐membered strong‐field chelate rings are coordinated to chiral six‐coordinate Cr(III) centers. In this minireview, we intend to focus our attention on the state‐of‐the‐art for the design of pseudo‐octahedral chiral mononuclear Cr(III) complexes for which chiroptical properties were investigated. The promising electronic properties of these complexes together with their low cost make these underexplored systems appealing candidates for CPL applications. [ABSTRACT FROM AUTHOR]

To improve current multiphase white light emitting diodes (WLEDs), a novel series of five complexes consisting of one binary and four ternary complexes that emitted cool white light was successfully synthesized using a chelating tetradentate ligand and auxiliary ligands, i.e. 5,6-dimethyl-1,10-phenanthroline, 1,10-phenanthroline, 4,40 - dimethyl-2,20 -bipyridyl, and 2,20 -bipyridyl. The series was examined structurally using elemental analysis, Fourier transform infrared spectroscopy, energy dispersive X-ray analysis, ultraviolet-visible spectroscopy, and proton nuclear magnetic resonance spectroscopy. These complexes had the appropriate thermal stability required for the generation of white organic LEDs (WOLEDs). Dysprosium (III) (Dy3+) ion complexes demonstrated the characteristic emission peaks of blue colour at 482 nm and yellow colour at 572 nm, respectively, when excited using near ultraviolet light. Band gap, refractive index, and decay lifetime of the optimized samples were recorded as 2.68 eV, 2.12, and 1.601 ms, respectively. Correlated colour temperature value (7875 K), Commission International de l'Eclairage coordinates (0.300, 0.294), and colour purity (21.04 x 10-2) of the optimized complex were near to those of white illuminants as defined by the National Television System Committee. These complexes had promise as commercial LEDs for the advanced optoelectronics devices, especially as WOLEDs for illumination applications. [ABSTRACT FROM AUTHOR]

A field‐induced chiral YbIII 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 2F5/2→2F7/2 emission while the NIR‐CPL is associated to the f‐f transitions of the YbIII ion bearing chiral β‐diketonate derived‐camphorate ancillary ligands. [ABSTRACT FROM AUTHOR]

Circularly polarized organic light‐emitting diodes (CP‐OLEDs) that enable circularly polarized luminescence (CPL) are promising for 3D display and photonic applications. However, the device efficiency and CPL character of CP‐OLEDs still lag behind the practical requirements. Here, two pairs of axially chiral emitting enantiomers, flexible (R/S)‐ODQPXZ and rigid (R/S)‐ODPPXZ, are reported by fusing (R/S)‐octahydro‐binaphthol chiral source, diphenyl quinoxaline (DQ)/dibenzo[a,c]phenazine (DP) acceptors and phenoxazine (PXZ) donors. The symmetrical chiral‐acceptor‐donor configuration endows them thermally activated delayed fluorescence (TADF) properties with small singlet–triplet energy gaps of 0.16 and 0.07 eV, high photoluminescence quantum yields of 92% and 89% in doped films, and obvious mirror‐image CPL characteristics, respectively. The CP‐OLEDs based on these TADF enantiomers not only show a maximum external quantum efficiency of 28.3% with yellow emission for (R/S)‐ODQPXZ and 20.3% with orange‐red emission for (R/S)‐ODPPXZ, but also display the CPL with dissymmetry factors (gEL) of 6.0 × 10−4 and 2.4 × 10−3, respectively. The high efficiency and obvious CPL of (R)‐ODPPXZ arise from a synergetic interplay of the TADF skeleton and the rigid coplanar acceptor for efficient chiral induction and suppressed intramolecular rotational quenching. [ABSTRACT FROM AUTHOR]

A series of highly emissive inert and chiral CrIII complexes displaying dual circularly polarized luminescence (CPL) within the NIR region have been prepared and characterized. The helical [Cr(dqpR)2]3+ (dqp=2,6‐di(quinolin‐8‐yl)pyridine; R=OCH3, Br or C≡CH) complexes were synthesized as racemic mixtures and resolved into their respective PP and MM enantiomers by chiral stationary phase HPLC. The corresponding enantiomers show large glum≈0.2 and high quantum yield of up to 17 %, which afford important CPL brightness of up to 170 m−1 cm−1, a key point for applications as chiral luminescent probes. Moreover, the long‐lived CP‐NIR emission provided by these chromophores (ms range) in aqueous solution opens the way toward the quantification of chiral targets in biological systems with time‐gated detection. Thus, such chiral chromophores based on earth abundant and inert 3d metals open new perspectives in the field of CPL and represent an alternative to precious 4d, 5d and to labile 4f metal‐based complexes. [ABSTRACT FROM AUTHOR]

A series of highly emissive inert and chiral CrIII complexes displaying dual circularly polarized luminescence (CPL) within the NIR region have been prepared and characterized. The helical [Cr(dqpR)2]3+ (dqp=2,6‐di(quinolin‐8‐yl)pyridine; R=OCH3, Br or C≡CH) complexes were synthesized as racemic mixtures and resolved into their respective PP and MM enantiomers by chiral stationary phase HPLC. The corresponding enantiomers show large glum≈0.2 and high quantum yield of up to 17 %, which afford important CPL brightness of up to 170 m−1 cm−1, a key point for applications as chiral luminescent probes. Moreover, the long‐lived CP‐NIR emission provided by these chromophores (ms range) in aqueous solution opens the way toward the quantification of chiral targets in biological systems with time‐gated detection. Thus, such chiral chromophores based on earth abundant and inert 3d metals open new perspectives in the field of CPL and represent an alternative to precious 4d, 5d and to labile 4f metal‐based complexes. [ABSTRACT FROM AUTHOR]

An ideal chelator for f‐elements features rapid kinetics of complexation, high thermodynamic stability, and slow kinetics of dissociation. Here we present the facile synthesis of a macrocyclic ligand bearing four 1‐hydroxy‐2‐pyridinone units linked to a cyclen scaffold that rapidly forms thermodynamically stable complexes with lanthanides (Sm3+, Eu3+, Tb3+, Dy3+) and a representative late actinide (Cm3+) in aqueous media and concurrently sensitizes them. Extended X‐ray absorption fine structure (EXAFS) spectroscopy revealed an increase in the Ln/An−O bond lengths following the trend Cm>Eu>Tb and EXAFS data were compatible with time‐resolved luminescence studies, which indicated one to two water molecules in the inner metal coordination sphere of Eu(III) and two water molecules for the Cm(III) complex. Spectrofluorimetric ligand competition titrations against DTPA confirmed the high thermodynamic stability of DOTHOPO complexes, with pM values between 19.9(1) and 21.9(2). [ABSTRACT FROM AUTHOR]

An increasing number of circularly polarized luminescence (CPL) molecular emitters has been developed in recent years and many of them are intended for applications in which high overall CPL efficiencies are required. In order to have a complete picture of the efficiency of a CPL emitter, dissymmetry factor (glum) is not enough. In the following we propose a new quantity, named CPL brightness (BCPL), which takes into account absorption extinction coefficient and quantum yield along with the glum factor. We calculated BCPL value for more than 180 compounds reported in the literature and we analyse data distribution for the main classes of CPL molecular emitters. This tool can be employed to put into context new CPL active compounds and to direct the choice of molecular systems for specific CPL applications. [ABSTRACT FROM AUTHOR]

H‐bonding driven J‐type aggregation and cooperative supramolecular polymerization of a sulfur‐substituted chiral naphthalene‐diimide (NDI)‐derivative (S,S)‐NDI‐2 in decane leads to remarkable enhancement of fluorescence quantum yield (43.3 % from 0.5 % in the monomeric state) and intense CPL signal in the aggregated state with a high luminescence dissymmetry factor (glum) of 4.6×10−2. A mixture of NDI‐2 with a structurally similar NDI‐derivative NDI‐1 (mixture of racemic (S,S)‐ and (R,R)‐ isomers and the achiral derivative) in 1:9 (NDI‐2/NDI‐1) ratio, when heated and slowly cooled to room temperature, showed no enhanced CD band, indicating lack of any preferential helicity. However, when a monomeric solution of the NDI‐1 in tetrahydrofuran (THF) was injected to preformed seed of NDI‐2 in decane, a prominent CD signal appeared, indicating chiral amplification resulting in induced CPL with high glum value of 2.0×10−2 from mostly (>98.5 %) diastereomeric mixture. [ABSTRACT FROM AUTHOR]

The syntheses of highly efficient NIR-emitting lanthanide complexes are challenging due to the lack of an effective strategy that can both simultaneously suppress the nonradiative transition caused by high energy oscillators and enhance the sensitization efficiency. Herein, a ditopic rigid Schiff base, N,N′-bisIJ2-oxy-3- methoxybenzylidene)-1,4-phenylenediamine (H2L), with p-phenylenediamine as a spacer was designed, which self-assembled with the Cd2+ and Ln3+ ions and TTA (2-thenoyltrifluoroacetone) forming tetranuclear Cd–Ln complexes, Ln2Cd2L2(TTA)4(OAc)2(CH3OH)2 (Ln = Nd (1), Yb (2) and La (3)). X-ray crystallographic analysis revealed that complex 1 adopted a double-stranded tetranuclear structure, in which the two heteronuclear Cd–Nd units were linked together by phenylene, and each NdIJIII) ion was nine-coordinated by four oxygen atoms from two L, four oxygen atoms from TTA and one oxygen atom from an acetate anion. The photophysical studies demonstrated that the helicates showed excellent NIR luminescence with the luminescence quantum yields reaching 0.34% for Nd3+ and 2.13% for Yb3+ in CH3- CN. The high NIR luminescence quantum yields benefit from the rigid structure of the complexes and the synergistic interactions between two ligands. Additionally, the large π-conjugating system of H2L makes the absorption edge of the complexes extend to the 450 nm blue light region, which makes the complexes suitable for biomedical applications. [ABSTRACT FROM AUTHOR]

Conjugated push‐pull molecules that incorporate nitrogen heterocycles as electron‐withdrawing units are interesting materials because of their luminescence properties. These chromophores can be easily and reversibly protonated at the nitrogen atom of the heterocyclic ring and this can cause dramatic color changes. White and multi‐color photoluminescence both in solution and in the solid state can be obtained by an accurate control of the amount of acid. Thus, with a suitable design these compounds have potential applications in the development of colorimetric pH sensors and the fabrication of OLEDs based on only one material. We provide here a brief overview of our collaborative efforts made in this area. [ABSTRACT FROM AUTHOR]

β-Diketones are one of the most widely used ligands for sensitizing the luminescence of lanthanide complexes due to their excellent sensitization abilities. However, the difficulties in introducing chiral groups to take part in the electronic transitions of conjugated systems limit their application in lanthanide circularly polarized luminescence (CPL) materials. In view of the inherent chirality of the helical structure, herein, a pair of homochiral quadruple-stranded helicates, Eu2L4, is assembled based on chiral bis-β-diketonate ligands, wherein the two point chirality centers in the spacer preorganize the helical conformation of the ligand (3S,4S)/(3R,4R)-3,4-bis(4,4′-bis(4,4,4-trifluoro-1,3-dioxobutyl)phenoxyl)-1-benzylpyrrolidine, LSS/LRR. X-ray crystallographic analyses reveal that the R,R configurations of the chiral carbons in the spacer induce the M helical sense of the ligand, while the S,S configurations induce the P helical sense. Through the comprehensive spectral characterization in combination with semiempirical geometry optimization using the Sparkle/RM1 model, it is confirmed that the preorganized ligands successfully control the homochirality of the helicates. Moreover, the mirror-image CD and CPL spectra and NMR measurements confirm the formation of enantiomeric pairs and their diastereopurities in solution. Detailed photophysical and chiroptical characterization studies reveal that the helicates not only exhibit intense circularly polarized luminescence (CPL) with ‖glum‖ values reaching 0.10, but also show a high luminescence quantum yield of 34%. This study effectively combines the helical chirality of the helicates with the excellent sensitization ability of the β-diketones, providing an effective strategy for the syntheses of chiral lanthanide CPL materials. [ABSTRACT FROM AUTHOR]

The chiral spin–flip luminophore [Cr(ddpd)2]3+ can be resolved into enantiopure material by chiral HPLC. The corresponding enantiomers show very high luminescence dissymmetry factors of up to ∣glum ∣≈ 0.093 in circularly polarized luminescence (CPL) measurements for the "ruby-like" phosphorescence transition 2E/2T1 → 4A2 in the near-IR region around λ ≈ 775 nm. [ABSTRACT FROM AUTHOR]

Chiroptical properties of two chiral atropisomers of propeller‐like trityl‐based radical derivatives have been analyzed. A new absolute configuration (AC) assignment has been made, according to the combination of experimental and theoretical data. In this sense, their ACs have been determined through the comparison of the Cotton effects recorded by electronic circular dichroism (ECD) with the theoretical ECD of the open shell structures obtained by TD‐DFT calculations. Finally, their circularly polarized luminescence (CPL) responses have been addressed. Remarkably, this is the first description of organic free radicals as intrinsic CPL emitters. Opposite signed CPL has been detected for each pair of conformers, with acceptable luminescent dissymmetry factors (|glum|≈0.5–0.8×10−3) considering their pure organic nature. In fact, highly efficient chiral emissions have been demonstrated, according to the comparison of |glum| with their respective absorption anisotropy factors (|gabs|). This pioneering study lays the foundations for the optimization of new magnetically active organic chiral emitters. [ABSTRACT FROM AUTHOR]

Chiroptical properties of two chiral atropisomers of propeller‐like trityl‐based radical derivatives have been analyzed. A new absolute configuration (AC) assignment has been made, according to the combination of experimental and theoretical data. In this sense, their ACs have been determined through the comparison of the Cotton effects recorded by electronic circular dichroism (ECD) with the theoretical ECD of the open shell structures obtained by TD‐DFT calculations. Finally, their circularly polarized luminescence (CPL) responses have been addressed. Remarkably, this is the first description of organic free radicals as intrinsic CPL emitters. Opposite signed CPL has been detected for each pair of conformers, with acceptable luminescent dissymmetry factors (|glum|≈0.5–0.8×10−3) considering their pure organic nature. In fact, highly efficient chiral emissions have been demonstrated, according to the comparison of |glum| with their respective absorption anisotropy factors (|gabs|). This pioneering study lays the foundations for the optimization of new magnetically active organic chiral emitters. [ABSTRACT FROM AUTHOR]

Chiroptical properties of two chiral atropisomers of propeller‐like trityl‐based radical derivatives have been analyzed. A new absolute configuration (AC) assignment has been made, according to the combination of experimental and theoretical data. In this sense, their ACs have been determined through the comparison of the Cotton effects recorded by electronic circular dichroism (ECD) with the theoretical ECD of the open shell structures obtained by TD‐DFT calculations. Finally, their circularly polarized luminescence (CPL) responses have been addressed. Remarkably, this is the first description of organic free radicals as intrinsic CPL emitters. Opposite signed CPL has been detected for each pair of conformers, with acceptable luminescent dissymmetry factors (|glum|≈0.5–0.8×10−3) considering their pure organic nature. In fact, highly efficient chiral emissions have been demonstrated, according to the comparison of |glum| with their respective absorption anisotropy factors (|gabs|). This pioneering study lays the foundations for the optimization of new magnetically active organic chiral emitters. [ABSTRACT FROM AUTHOR]

Quinoline oligoamide foldamers appended with non-chiral fluorophores and derivatized with a camphanyl chiral inducer display strong chiroptical properties at tunable wavelengths as proved by CD and CPL spectroscopies. Induced CPL activity with high luminescence dissymmetry factors was observed in the visible range at wavelengths specific to the fluorophores. [ABSTRACT FROM AUTHOR]

Chiral materials with circularly polarized luminescence (CPL) are potentially applicable for 3D displays. In this study, by decorating the pyridinyl‐helicene ligands with ‐CF3 and ‐F groups, the platinahelicene enantiomers featured superior configurational stability, as well as high sublimation yield (>90 %) and clear CPPL properties, with dissymmetry factors (|gPL|) of approximately 3.7×10−3 in solution and about 4.1×10−3 in doped film. The evaporated circularly polarized phosphorescent organic light‐emitting diodes (CP‐PhOLEDs) with two enantiomers as emitters exhibited symmetric CPEL signals with |gEL| of (1.1–1.6)×10−3 and decent device performances, achieving a maximum brightness of 11 590 cd m−2, a maximum external quantum efficiency up to 18.81 %, which are the highest values among the reported devices based on chiral phosphorescent PtII complexes. To suppress the effect of reverse CPEL signal from the cathode reflection, the further implementation of semitransparent aluminum/silver cathode successfully boosts up the |gEL| by over three times to 5.1×10−3. [ABSTRACT FROM AUTHOR]

Abstract: Circularly polarised luminescence (CPL) is a chiroptical phenomenon gaining more and more attention, as the availability of the necessary spectrometers is getting better and first applications in bioimaging or for the preparation of OLEDs (organic light emitting diodes) are coming within range. Until now most examples of distinctly CPL‐active compounds were europium and terbium complexes though theoretically the electronic structure of samarium should be as suitable as the one of terbium. This discrepancy can be accounted for by the high susceptibility of samarium to non‐radiative deactivation processes. The aim of this study was to strategically circumvent this difficulty by the use of a ligand scaffold which has already proven to efficiently suppress these processes, namely the cryptates. The prepared partly deuterated samarium and europium complexes exhibit distinct circularly polarised luminescence with dissymmetry factors up to glum=+0.13 (SmIII) or glum=−0.19 (EuIII). [ABSTRACT FROM AUTHOR]

Abstract: In this paper we designed a kind of aggregation‐induced emission (AIE) chiral fluorescence emitters (R/S‐BINOL‐CN enantiomers) in the aggregate state. Chiral emissive nematic liquid crystals (N*‐LCs) prepared by doping this kind of AIE‐active R/S‐BINOL‐CN enantiomers into a common achiral nematic liquid crystal (N‐LC, E7) can self‐assemble as the regularly planar Grandjean texture leading to high luminescence dissymmetry factor (glum) of aggregation‐induced circularly polarized luminescence (AI‐CPL) signal up to 0.41, which can be attributed to dipolar interactions from polar cyano groups and π–π interactions between binaphthyl moiety of the dopant R/S‐BINOL‐CN and biphenyl group of the host molecules (E7). [ABSTRACT FROM AUTHOR]

Abstract: Two series of isostructural lanthanide coordination complexes, namely, LIFM‐42(Ln) (Ln=Eu, Tb, Gd, in which LIFM stands for the Lehn Institute of Functional Materials) and LIFM‐43(Ln) (Ln=Er, Yb), were synthesized through the self‐assembly of an excited‐state intramolecular proton transfer (ESIPT) ligand, 5‐[2‐(5‐fluoro‐2‐hydroxyphenyl)‐4,5‐bis(4‐fluorophenyl)‐1H‐imidazol‐1‐yl]isophthalic acid (H2hpi2cf), with different lanthanide ions. In the coordination structures linked by the ligands and oxo‐bridged LnIII2 clusters (for LIFM‐42(Ln) series) or isolated LnIII ions (for LIFM‐43(Ln) series), the ESIPT ligand can serve as both the host and antenna for protecting and sensitizing the photoluminescence (PL) of LnIII ions. Meanwhile, the −OH⋅⋅⋅N active sites on the ligands are vacant, which provides availability to systematically explore the PL behavior of Ln complexes with ESIPT interference. Based on the accepting levels of different lanthanide ions, energy transfer can occur from the T1(K*) or T1(E*) (K*=excited keto form, E*=excited enol form) excited states of the ligand. Furthermore, the sensitized lanthanide luminescence in both visible and near‐infrared regions, as well as the remaining K* emission of the ligand, can be modulated by the ESIPT responsiveness to different solvents, anions, and temperature. [ABSTRACT FROM AUTHOR]

We studied enantiopure chiral trivalent lanthanide (Ln3+ = La3+, Sm3+, Eu3+, Gd3+, Tm3+, and Yb3+) complexes with two fluorinated achiral tris(β-diketonate) ligands (HFA = hexafluoroacetylacetonate and TTA = 2-thenoyltrifluoroacetonate), incorporating a chiral bis(oxazolinyl)pyridine (PyBox) unit as a neutral ancillary ligand, by the combined use of optical and chiroptical methods, ranging from UV to IR both in absorption and circular dichroism (CD), and including circularly polarized luminescence (CPL). Ultimately, all the spectroscopic information is integrated into a total and a chiroptical super-spectrum, which allows one to characterize a multidimensional chemical space, spanned by the different Ln3+ ions, the acidity and steric demand of the diketone and the chirality of the PyBox ligand. In all cases, the Ln3+ ions endow the systems with peculiar chiroptical properties, either allied to f–f transitions or induced by the metal onto the ligand. In more detail, we found that Sm3+ complexes display interesting CPL features, which partly superimpose and partly integrate the more common Eu3+ properties. Especially, in the context of security tags, the pair Sm/Eu may be a winning choice for chiroptical barcoding. [ABSTRACT FROM AUTHOR]

A star‐shaped molecule with a central electron‐deficient triazine ring connected to three electron‐rich N‐annulated perylene tetraesters was synthesized. Its application as an emissive layer in the fabrication of a sole and host–guest solution processable OLED, exhibiting bright green emission with good electroluminescence efficiency is demonstrated. [ABSTRACT FROM AUTHOR]

Abstract: Aromatic‐imide‐based thermally activated delayed fluorescent (TADF) enantiomers, (+)‐(S,S)‐CAI‐Cz and (−)‐(R,R)‐CAI‐Cz, were efficiently synthesized by introducing a chiral 1,2‐diaminocyclohexane to the achiral TADF unit. The TADF enantiomers exhibited high PLQYs of up to 98 %, small ΔEST values of 0.06 eV, as well as obvious temperature‐dependent transient PL spectra, thus demonstrating their excellent TADF properties. Moreover, the TADF enantiomers showed mirror‐image CD and CPL activities. Notably, the CP‐OLEDs with CPEL properties based on the TADF enantiomers not only achieved high EQE values of up to 19.7 and 19.8 %, but also displayed opposite CPEL signals with gEL values of −1.7×10−3 and 2.3×10−3, which represents the first CP‐OLEDs, based on the enantiomerically pure TADF materials, having both high efficiencies and intense CPEL. [ABSTRACT FROM AUTHOR]

A series of copper(I) complexes bearing a bis(diphenylphosphoryl)amide (dppaO2-) ligand and a diphosphine ligand were synthesized, and their photophysical properties were investigated. Two complexes, [Cu(dppaO2)(DPEphos)] {DPEphos = bis[2-(diphenylphosphanyl)phenyl] ether} and [Cu(dppaO2)(XANTPHOS)] [XANTPHOS = 9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene], show bright white-blue and deep blue luminescence, respectively, in the solid state. The quantum yield of [Cu(dppaO2)(XANTPHOS)] is 0.76 under argon and 0.38 under air. The emission decay curves under argon [ τ = 7.9 (17 %), 30.0 µs (83 %)] in the solid state are longer than those under air [ τ = 2.5 (19 %), 13.9 µs (81 %)]. The photophysical properties of the complexes are discussed together with the results of DFT and time-dependent DFT (TD-DFT) calculations. [ABSTRACT FROM AUTHOR]

Three NIR-emitting neutral IrIII complexes [Ir(iqbt)2(dpm)] ( 1), [Ir(iqbt)2(tta)] ( 2), and [Ir(iqbt)2(dtdk)] ( 3) based on the 1-(benzo[b]thiophen-2-yl)-isoquinolinate (iqtb) were synthesized and characterized (dpm=2,2,6,6-tetramethyl-3,5-heptanedionate; tta=2-thienoyltrifluoroacetonate; dtdk=1,3-di(thiophen-2-yl)propane-1,3-dionate). The compounds emit between λ=680 and 850 nm with high luminescence quantum yields (up to 16 %). By combining electrochemistry, photophysical measurements, and computational modelling, the relationship between the structure, energy levels, and properties were investigated. NIR-emitting, solution-processed phosphorescent organic light-emitting devices (PHOLEDs) were fabricated using the complexes. The devices show remarkable external quantum efficiencies (above 3 % with 1) with negligible efficiency roll-off values, exceeding the highest reported values for solution-processible NIR emitters. [ABSTRACT FROM AUTHOR]

New fluorescent D-A-D dyes containing 9-(p-tolyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole as a donor unit and 2,1,3-benzochalcogenadiazoles as an electron-withdrawing group were synthesized. The photoluminescent and electroluminescent properties of novel dyes for fluorescent OLED application were investigated. It was demonstrated that the replacement of lightweight heteroatoms by heavier ones enables the fine tuning of the maximum emission without significantly reducing the luminescence quantum yield. The maximum quantum yield value of 62.6% for derivatives based on 2,1,3-benzoxadiazole (1a) in cyclohexane was achieved. Two devices with the architecture of glass/ITO/PEDOT-PSS/poly-TPD/EML/TPBi/LiF/Al (EML = emitting layer) were fabricated to check the suitability of the synthesized compounds as a single active emission layer in OLED. These OLEDs exhibited clear red electroluminescence of the dyes with the maximum current efficiency of 0.85 Cd/A. [ABSTRACT FROM AUTHOR]