Endowing Metal-Organic Coordination Materials with Chiroptical Activity by a Chiral Anion Strategy.

Recently, chiral metal-organic coordination materials have emerged as promising candidates for a wide range of applications in chiroptoelectronics, chiral catalysis, and information encryption, etc. Notably, the chiroptical effect of coordination chromophores makes them appealing for applications such as photodetectors, OLEDs, 3D displays, and bioimaging. The direct synthesis of chiral coordination materials using chiral organic ligands or complexes with metal-centered chirality is very often tedious and costly. In the case of ionic coordination materials, the combination of chiral anions with cationic, achiral coordination compounds through noncovalent interactions may endow molecular materials with desirable chiroptical properties. The use of such a simple chiral strategy has been proven effective in inducing promising circular dichroism and/or circularly polarized luminescence signals. This concept article mainly delves into the latest advances in exploring the efficacy of such a chiral anion strategy for transforming achiral coordination materials into chromophores with superb photo- or electro-chiroptical properties. In particular, ionic small-molecular metal complexes, metal clusters, coordination supramolecular assemblies, and metal-organic frameworks containing chiral anions are discussed. A perspective on the future opportunities on the preparation of chiroptical materials with the chiral anion strategy is also presented.

Boost the Circularly Polarized Phosphorescence of Chiral Organometallic Platinum Complexes by Hierarchical Assembly into Fibrillar Networks.

Circularly polarized luminescence (CPL)-active molecular materials have drawn increasing attention due to their promising applications for next-generation display and optoelectronic technologies. Currently, it is challenging to obtain CPL materials with both large luminescence dissymmetry factor (glum) and high quantum yield (Φ). A pair of enantiomeric N N C-type Pt(II) complexes (L/D)-1 modified with chiral Leucine methyl ester are presented herein. Though the solutions of these complexes are CPL-inactive, the spin-coated thin films of (L/D)-1 exhibit giantly-amplified circularly polarized phosphorescences with |glum| of 0.53 at 560 nm and Φair of ~50 %, as well as appealing circular dichroism (CD) signals with the maximum absorption dissymmetry factor |gabs| of 0.37-0.43 at 480 nm. This superior CPL performance benefits from the hierarchical formation of crystalline fibrillar networks upon spin coating. Comparative studies of another pair of chiral Pt(II) complexes (L/D)-2 with a symmetric N C N coordination mode suggest that the asymmetric N N C coordination of (L/D)-1 are favorable for the efficient exciton delocalization to amplify the CPL performance. Optical applications of the thin films of (L/D)-1 in CPL-contrast imaging and inducing CP light generation from achiral emitters and common light-emitting diode lamps have been successfully realized.

Vaporchromic Domino Transformation and Polarized Photonic Heterojunctions of Organoplatinum Microrods.

Photonic heterostructures with codable properties have shown great values as versatile information carriers at the micro and nanoscale. These heterostructures are typically prepared by a step-by-step growth or post-functionalization method to achieve varied emission colors among different building blocks. In order to realize high-throughput and multivariate information loading, we report here a strategy to integrate polarization signals into photonic heterojunctions. A U-shaped di-Pt(II) complex is assembled into highly-polarized yellow-phosphorescent crystalline microrods (Y-rod) by strong intermolecular Pt···Pt interaction. Upon end-initiated desorption of the incorporated CH2Cl2 solvents, Y-rod is transformed in a domino fashion into tri-block polarized photonic heterojunctions (PPHs) with alternate red-yellow-red emissions or red-phosphorescent microrods (R-rod). The red emissions of these structures are also highly polarized; however, their polarization directions are just orthogonal to those of the yellow phosphorescence of Y-rod. With the aid of a patterned mask, R-rod is further programmed into multi-block PPHs with precisely-controlled block sizes by side-allowed adsorption of CH2Cl2 vapor. X-ray diffraction analysis and theoretical calculations suggest that the solvent-regulated modulation of intramolecular and intermolecular excited states is critical for the construction of these PPHs.

Synchronously Improved Multiple Afterglow and Phosphorescence Efficiencies in 0D Hybrid Zinc Halides with Ultrahigh Anti-Water Stabilities.

Zero-dimensional (0D) hybrid metal halides have been emerged as room-temperature phosphorescence (RTP) materials, but synchronous optimization of multiple phosphorescence performance in one structural platform remains less resolved, and stable RTP activity in aqueous medium is also unrealized due to serious instability toward water and oxygen. Herein, we demonstrated a photophysical tuning strategy in a new 0D hybrid zinc halide family of (BTPP)2ZnX4 (BTPP = benzyltriphenylphosphonium, X = Cl and Br). Infrequently, the delicate combination of organic and inorganic species enables this family to display multiple ultralong green afterglow and efficient self-trapped exciton (STE) associated cyan phosphorescence. Compared with inert luminescence of [BTPP]+ cation, incorporation of anionic [ZnX4]2- effectively enhance the spin-orbit coupling effect, which significantly boosts the photoluminescence quantum yield (PLQY) up to 30.66% and 54.62% for afterglow and phosphorescence, respectively. Synchronously, the corresponding luminescence lifetime extend to 143.94 ms and 0.308 µs surpassing the indiscernible phosphorescence of [BTPP]X salt. More importantly, this halide family presents robust RTP emission with nearly unattenuated PLQY in water and harsh condition (acid and basic aqueous solution) over half a year. The highly efficient integrated afterglow and STE phosphorescence as well as ultrahigh aqueous state RTP realize multiple anti-counterfeiting applications in wide chemical environments.

Electrically Amplified Circularly Polarized Luminescence by a Chiral Anion Strategy.

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.

Organoplatinum(II) Cruciform: A Versatile Building Block to Fabricate 2D Microcrystals with Full-Color and White Phosphorescence and Anisotropic Photon Transport.

Conventional square-planar platinum complexes typically form one-dimensional assemblies as a result of unidirectional metallophilic and/or π⋅⋅⋅π intermolecular interactions. Organoplatinum(II) complexes with a cruciform shape are presented herein to construct two-dimensional (2D) microcrystals with full-color and white phosphorescence. These 2D crystals show unique monocomponent π⋅⋅⋅π stacking, from either the cyclometalating or noncyclometalating ligand, and the bicomponent alternate π⋅⋅⋅π stacking from both ligands along different facet directions. Anisotropic tri-directional waveguiding is further implemented on a single hexagonal microcrystal. These results demonstrate the great capability of the organoplatinum(II) cruciform as a general platform to fabricate 2D phosphorescent micro-/nanocrystals for advanced photonic applications.

Selective, Anisotropic, or Consistent Polarized-Photon Out-Coupling of 2D Organic Microcrystals.

Nano- and micromaterials with anisotropic photoluminescence and photon transport have widespread application prospects in quantum optics, optoelectronics, and displays. But the nature of the polarization information of the out-coupled light, with respect to that of the source luminescence, has never been explored in active optical-waveguiding organic crystals. Herein, three different modes (selective, anisotropic, and consistent) of polarized-photon out-coupling are proposed and successfully implemented in a set of 2D organic microcrystals with highly linearly-polarized luminescence. It is found that the polarization direction and degree of the luminescence out-coupled through different waveguiding channels can either be essentially retained or distinctly changed with respect to those of the original luminescence, depending on the molecular arrangement and the orientation of transition dipole moments of the crystal. This work demonstrates the promising potential of 2D emissive microcrystals in multi-channel polarized photon transport.

A Carbazole-Bridged Biscyclometalated Diplatinum Complex: Synthesis, Characterization, and Dual-Mode Aggregation-Enhanced Phosphorescence.

A cationic carbazole-bridged biscyclometalated diplatinum complex 4 has been synthesized and characterized. Single-crystal X-ray analysis demonstrates that complex 4 displays a dimeric structure with noncovalent π-π stacking and unique double Pt-Pt interactions. In aerated dilute CH3CN, complex 4 is characterized by a very weak monomeric yellow emission (λemi = 547 nm; Φ = 0.51%), which is attributed to the triplet intraligand (3LC) excited state mixing with some charge transfer characters. In contrast, under aerated conditions, the dispersion of 4 in a mixed solvent of CH3CN/Et2O (1/9, v/v) or CH3CN/H2O (1/9, v/v) displays intense yellow (λemi = 550 nm; Φ = 35.5%; τ = 11.10 µs) and red emission (λemi = 635 nm; Φ = 14.1%; τ = 7.00 µs), respectively. These aggregation-induced phosphorescent emission enhancements are considered being caused by the oxygen-shielding effect and the molecular rigidification-induced decrease of nonradiative decays in the aggregate state. The morphology and size of the aggregates under these two conditions are examined by scanning electron microscope and dynamic light scattering analysis. The absorption and emission properties of 4 are further rationalized by time-dependent density functional theory calculations on a model compound.

Dual-Emissive Tris-Heteroleptic Ruthenium Complexes: Tuning the DNA-Triggered Ratiometric Emission Response by Ancillary Ligands.

Three tris-heteroleptic mononuclear Ru(II) complexes with dual fluorescence and phosphorescence-[Ru(dpma)(bpy)(phen)]2+ (12+), [Ru(dpma)(bpy)(dppz)]2+ (22+), and [Ru(dpma)(phen)(dppz)]2+ (32+)-have been designed and used as ratiometric light-response probes for DNA, where dpma is di(pyrid-2-yl)(methyl)-amine, bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline, and dppz is dipyridophenazine, respectively. Single crystals of complex 2(PF6)2 have been obtained and studied by X-ray analysis. The interactions of these complexes with different DNAs are investigated by means of spectroscopic methods, viscosity measurements, and molecular modeling. In the presence of calf thymus DNA, complexes 2(PF6)2 and 3(PF6)2 show the emergence of a new lower-energy phosphorescence emission band; meanwhile, the higher-energy fluorescence emission band is essentially unchanged, functioning as an intrinsic internal reference. These two complexes exhibit stronger preference for calf thymus DNA over single-strand DNA (d(A)16 and d(C)16). In contrast, no binding interaction between 1(PF6)2 and calf thymus DNA is observed. The intrinsic binding constants (Kb) of 2(PF6)2 and 3(PF6)2 with calf thymus DNA are determined to be (1.4 ± 0.4) × 105 and (9.5 ± 0.15) × 104 M-1, respectively. In addition, these spectroscopic results are compared with those of the prototype complex [Ru(bpy)2(dppz)]2+ (42+), and density functional theory and time-dependent density functional theory calculations are employed to elucidate these experimental findings.

Full-Color and White Circularly Polarized Luminescence of Hydrogen-Bonded Ionic Organic Microcrystals.

A simple and general method is presented herein for the in situ preparations of circularly polarized luminescence (CPL)-active microcrystals with a large luminescence dissymmetry factor glum , high fluorescence quantum efficiency (ΦFL ), wide emission color tenability, and well-ordered morphology. The reactions of pyridine-containing achiral molecules 1-7 with chiral camphor sulfonic acid ((±)-CSA) gave crystalline microplates formed by hydrogen bonding interactions between the protonated pyridinium units and the sulfonic anions. The chiral information of CSA are effectively transferred to the microcrystals by hydrogen bonding to afford full-color CPL from deep-blue to red with glum in the order of 10-2 and ΦFL up to 80 %. Moreover, organic microcrystals with high-performance white CPL (ΦFL =46 %; |glum |=0.025) are achieved via the light-harvesting energy transfer between blue and yellow emitters.

Effect of the Fluoro-Substituent Position on the Crystal Structure and Photoluminescence of Microcrystals of Platinum ß-Diketonate Complexes.

Molecular packing has an important effect on the photophysical properties of crystalline materials. We demonstrate in this work the modulation of molecular packing and emission properties of microcrystals by minor molecular structural variations. Four platinum ß-diketonate complexes, with two fluoro substituents (1) or one fluoro atom substituted on different positions of the auxiliary phenylpyridine ligand (2-4) have been synthesized. These complexes were used to prepare one-dimensional microcrystals with well-defined shapes and uniform sizes. Although 1-4 display similar emission spectra in the solution state, the corresponding microcrystals display different emission colors from green to yellow and orange. In addition, different temperature-responsive (80-298 K) emission spectral changes have been observed from these microcrystals, including the intensity variation of the locally excited (LE) emission without obvious wavelength shifts, competition between the LE and metal-metal-to-ligand charge-transfer emissions, and the sole wavelength shift of the π-π excimer emissions. These differences in emission properties are rationalized by different molecular packings of these materials, as revealed by single-crystal X-ray analyses.

Temperature-Triggered Self-Assembled Structural Transformation: From Pure Hydrogen-Bonding Quadrilateral Nanonetwork to Trihexagonal Structures.

Adequate control over the structures of molecular building blocks plays an important role in the fabrication of desired supramolecular nanostructures at interfaces. In this study, the formation of a pure hydrogen-bonding co-assembly supramolecular nanonetwork on a highly oriented pyrolytic graphite surface was demonstrated by means of a scanning tunneling microscope. The thermal annealing process was conducted to monitor the temperature-triggered structural transformation of the self-assembled nanonetwork. On the basis of the single-molecule-level resolution scanning tunneling microscopy images, together with the density functional theory calculations, the formation mechanisms of the formed nanoarrays were proposed. The results have great significance with regard to controlled construction of complex nanostructures on the surface.

Temperature-Responsive Fluorescent Organoplatinum(II) Metallacycles.

The synthesis, characterization, and temperature-responsive properties of two fluorescent organoplatinum(II) metallacycles are reported. Metallacycles M1 and M2 were prepared via the coordination-driven self-assembly of a 120° triarylamine ligand L1 and a 120° diplatinum(II) acceptor Pt-1 or 180° diplatinum(II) acceptor Pt-2, respectively. M1 and M2 are hexagonal metallacycles, comprising of three or six freely rotating anthracene pendants on their periphery, respectively. In response to the temperature variation between -20 and 60 °C, the ligand displays irregular emission changes, whereas both metallacycles show reversible absorption and emission spectral changes in THF. The changes in their green emission intensity also exhibit a linear correlation with the temperature variation, with an average sensitivity of -0.67% and -0.77% per °C for M1 and M2, respectively. Furthermore, in coordinating solvents, such as DMF and CH3CN, M1 and M2 show different behaviors: in the lower temperature range, i.e., below 30 °C, their spectral changes are similar to those observed in THF; however, at a higher temperature the metallacycles were presumably destroyed by the solvents and displayed ratiometric fluorescent responses, including a cyan emission of the ligand L1.

Anion-regulated electronic communication in a cyclometalated diruthenium complex with a urea bridge.

A combined study of electrochemical measurements, intervalence charge transfer analysis, and DFT calculations suggests that the degree of urea-mediated electronic coupling between two cyclometalated ruthenium sites is enhanced by the coordination of urea with Br- or Cl-via hydrogen bonding. In contrast, the redox waves of the diruthenium complex become highly irreversible in the presence of relatively strong basic anions such as H2PO4-, F-, or OAc-. This work demonstrates that the anion-urea interaction can be employed to regulate the electronic coupling and electron transfer between redox-active sites, suggesting the potential applications of the urea-functionalized diruthenium complex in anion sensing and stimuli-responsive molecular electronics.

H2PO4-- and Solvent-Induced Polymorphism of an Amide-Functionalized [Pt(N

A simple [Pt(N^C^N)Cl] complex functionalized with an amide group was prepared, and its absorption and emission properties were examined in different solvents in response to various anions. On the one hand, in the presence of H2PO4-, the solution of the complex shows distinct color changes in CH3CN, together with a ratiometric emission change from a green emission band at 537 nm to a deep red emission band at 680 nm. On the other hand, two-step spectral changes were observed in response to H2PO4- in CH2Cl2, with the green emission being attenuated first followed by the appearance of enhanced and yellow-green emissions at a lower-energy region. These recognition processes are highly selective for H2PO4- against other common anions including F-, Cl-, Br-, I-, OAc-, NO3-, and HSO4-. In addition, the platinum complex displays multistage emission polymorphism in mixed CH3CN/H2O solvent of various ratios. The hydrogen-bonding interaction between H2PO4- and the amide unit was confirmed by NMR analysis. In the solid state, this platinum complex emits red light. However, the composite material of the platinum complex with H2PO4- shows purely monomeric yellow emissions. The solid-state materials were further analyzed by single-crystal X-ray and Fourier-transform IR analysis. These studies suggest that this simple platinum complex is useful for the selective recognition of H2PO4- and as solid-state emitting materials with tunable emission colors.

Molecular Conductance through a Quadruple-Hydrogen-Bond-Bridged Supramolecular Junction.

A series of self-complementary ureido pyrimidinedione (UPy) derivatives modified with different aurophilic anchoring groups were synthesized. Their electron transport properties through the quadruple hydrogen bonds in apolar solvent were probed employing the scanning tunneling microscopy break junction (STMBJ) technique. The molecule terminated with a thiol shows the optimal electron transport properties, with a statistical conductance value that approaches 10(-3)  G0 . The (1) H NMR spectra and control experiments verify the formation of quadruple hydrogen bonds, which can be effectively modulated by the polarity of the solvent environment. These findings provide a new design strategy for supramolecular circuit elements in molecular electronics.

Conformation-determined through-bond versus through-space electronic communication in mixed-valence systems with a cross-conjugated urea bridge.

Bis-triarylamine 2 and cyclometalated diruthenium 6(PF6)2 with a linear trans,trans-urea bridge have been prepared, together with the bis-triarylamine 3 and cyclometalated diruthenium 8(PF6)2 with a folded cis,cis-N,N-dimethylurea bridge. The linear or folded conformations of these molecules are supported by single-crystal X-ray structures of 2, 3, and other related compounds. These compounds display two consecutive anodic redox waves (N(·+/0) or Ru(III/II) processes) with a potential separation of 110-170 mV. This suggests that an efficient electronic coupling is present between two redox termini through the cross-conjugated urea bridge. The degree of electronic coupling has been investigated by using spectroelectrochemical measurements. Distinct intervalence charge-transfer (IVCT) transitions have been observed for mixed-valent (MV) compounds with a linear conformation. The IVCT transitions can also be identified for the folded MV compounds, albeit with a much weaker intensity. DFT results support that the electronic communication occurs by a through-bond and through-space pathway for the linear and folded compounds, respectively. The IVCT transitions of the MV compounds have been reproduced by TDDFT calculations. For the purpose of comparison, a bistriarylamine and a diruthenium complex with an imidazolidin-2-one bridge and a urea-containing mono-triarylamine and monoruthenium complex have been synthesized and studied.

Cyclometalated Osmium-Amine Electronic Communication through the p-Oligophenylene Wire.

A series of bis-tridentate cyclometalated osmium complexes with a redox-active triarylamine substituent have been prepared, where the amine substituent is separated from the osmium ion by a p-oligophenylene wire of various lengths. X-ray crystallographic data of complexes 3(PF6) and 4(PF6) with three or four repeating phenyl units between the osmium ion and the amine substituent are presented. These complexes show two consecutive anodic redox couples between +0.1 and +0.9 V vs Ag/AgCl, with the potential splitting in the range of 300-390 mV. A combined experimental and theoretical study suggests that, in the one-electron-oxidized state, the odd electron is delocalized for short congeners and localized on the osmium component for long congeners. The electronic coupling parameter (Vab) was estimated by the Marcus-Hush analysis. The distance dependence plot of ln(Vab) versus the osmium-amine geometrical distance (Rab) gives a negative linear relationship with a decay slope of -0.19 Å(-1), which is slightly steeper with respect to the previously reported ruthenium-amine series with the same molecular wire. DFT calculations with the long-range-corrected UCAM-B3LYP functional gave more reasonable results for the osmium complexes with respect to those with UB3LYP.

Nylons with Highly-Bright and Ultralong Organic Room-Temperature Phosphorescence.

Endowing the widely-used synthetic polymer nylon with high-performance organic room-temperature phosphorescence would produce advanced materials with a great potential for applications in daily life and industry. One key to achieving this goal is to find a suitable organic luminophore that can access the triplet excited state with the aid of the nylon matrix by controlling the matrix-luminophore interaction. Herein we report highly-efficient room-temperature phosphorescence nylons by doping cyano-substituted benzimidazole derivatives into the nylon 6 matrix. These homogeneously doped materials show ultralong phosphorescence lifetimes of up to 1.5 s and high phosphorescence quantum efficiency of up to 48.3% at the same time. The synergistic effect of the homogeneous dopant distribution via hydrogen bonding interaction, the rigid environment of the matrix polymer, and the potential energy transfer between doped luminophores and nylon is important for achieving the high-performance room-temperature phosphorescence, as supported by combined experimental and theoretical results with control compounds and various polymeric matrices. One-dimensional optical fibers are prepared from these doped room-temperature phosphorescence nylons that can transport both blue fluorescent and green afterglow photonic signals across the millimeter distance without significant optical attenuation. The potential applications of these phosphorescent materials in dual information encryption and rewritable recording are illustrated.

Dual-Emissive Monoruthenium Complexes of N(CH3)-Bridged Ligand: Synthesis, Characterization, and Substituent Effect.

Three monoruthenium complexes 1(PF6)2-3(PF6)2 bearing an N(CH3)-bridged ligand have been synthesized and characterized. These complexes have a general formula of [Ru(bpy)2(L)](PF6)2, where L is a 2,5-di(N-methyl-N'-(pyrid-2-yl)amino)pyrazine (dapz) derivative with various substituents, and bpy is 2,2'-bipyridine. The photophysical and electrochemical properties of these compounds have been examined. The solid-state structure of complex 3(PF6)2 is studied by single-crystal X-ray analysis. These complexes show two well-separated emission bands centered at 451 and 646 nm (Δλmax = 195 nm) for 1(PF6)2, 465 and 627 nm (Δλmax = 162 nm) for 2(PF6)2, and 455 and 608 nm (Δλmax = 153 nm) for 3(PF6)2 in dilute acetonitrile solution, respectively. The emission maxima of the higher-energy emission bands of these complexes are similar, while the lower-energy emission bands are dependent on the electronic nature of substituents. These complexes display two consecutive redox couples owing to the stepwise oxidation of the N(CH3)-bridged ligand and ruthenium component. Moreover, these experimental observations are analyzed by computational investigation.