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.

Photoelectrochemical Cells with a Pyridine-Anchored Bilayer Photoanode for Water Splitting.

A dye-sensitized photoanode is prepared by coassembling a Ru complex photosensitizer and a Ru water oxidation catalyst (WOC) on a TiO2 substrate, in which the WOC molecules are immobilized in a layer-by-layer fashion through metal-pyridine coordination with the aid of a bifunctional anchoring and bridging molecule containing multiple pyridine groups. Under visible-light irradiation, an anodic photocurrent of around 200 µA/cm2 has been achieved with O2 and H2 being generated at the photoanode and Pt counter electrode, respectively. The pyridine anchoring strategy provides a simple method to prepare photoelectrodes for applications in photoelectrochemical cells.

A Multi-Pyridine-Anchored and -Linked Bilayer Photocathode for Water Reduction.

The development of efficient photocathodes is of critical importance for the constructions of promising tandem photo-electrochemical cells. Most known dye-sensitized photocathodes are prepared with the conventional carboxylic or phosphonic acid anchors and require the presence of other terminal linking groups to connect catalysts; they suffer from high synthetic difficulty and low adsorption stability in aqueous media. Here, a compact bilayer photocathode has been prepared by using a pyrene-based photosensitizer with multiple terminal pyridine moieties as both the anchoring and linking groups to connect a Co hydrogen-evolution catalyst to the NiO substrate. The catalyst and dye molecule are assembled in a layer-by-layer manner on NiO through the metal-pyridine coordination. This photocathode exhibits good dye adsorption stability in aqueous media. A stable cathodic photocurrent of 70 µA cm-2 was achieved, with H2 being generated at the photocathode under the visible-light irradiation. The Faraday efficiency of H2 evolution was estimated to be 9.1 %. Transient absorption spectral studies suggest that the interfacial hole transfer occurs within a few picoseconds. The integration of the organic photosensitizer with pyridine anchoring and linking groups is expected to provide a simple method for the fabrication of stable and efficient photocathodes.

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.

Photoelectrochemical cells with a pyridine-anchored organic dye photoanode for efficient H2 generation by water reduction.

TiO2 photoelectrodes modified with organic dyes with pyridine anchoring groups are prepared, which are used as photoanodes of dye-sensitized photoelectrochemical cells for efficient water reduction with high photocurrent density and stability in aqueous solutions. Vigorous H2 generation with a production rate of around 250 µmol h-1 is realized with a photoanode of an active area of 5 × 5 cm2.

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.

Robust singlet fission process in strong absorption π-expanded diketopyrrolopyrroles.

Singlet fission (SF) has drawn tremendous attention as a multiexciton generation process that could mitigate the thermal loss and boost the efficiency of solar energy conversion. Although a SF-based solar cell with an EQE above 100% has already been fabricated successfully, the practical efficiency of the corresponding devices is plagued by the limited scope of SF materials. Therefore, it is of great importance to design and develop new SF-capable compounds aiming at practical device application. In the current contribution, via a π-expanded strategy, we presented a new series of robust SF chromophores based on polycyclic DPP derivatives, Ex-DPPs. Compared to conventional DPP molecules, Ex-DPPs feature strong absorption with a fivefold extinction coefficient, good molecular rigidity to effectively restrain non-radiative deactivation, and an expanded π-skeleton which endow them with well-suited intermolecular packing geometries for achieving efficient SF process. These results not only provide a new type of high-efficiency SF chromophore but also address some basic guidelines for the design of potential SF materials targeting practical light harvesting 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.

Bridge-Length- and Solvent-Dependent Charge Separation and Recombination Processes in Donor-Bridge-Acceptor Molecules.

The photoinduced intramolecular charge separation (CS) and charge recombination (CR) phenomena in a series of donor-bridge-acceptor (D-B-A) molecules are intensively investigated as a means of understanding electron transport through the π-B. Pyrene (Pyr) and triarylamine (TAA) moieties connected via phenylene Bs of various lengths are studied because their CS and CR behaviors can be readily monitored in real time by femtosecond transient absorption (fs-TA) spectroscopy. By combining the steady-state and fs-TA spectroscopic measurements in a variety of solvents together with chemical calculations, the parameters that govern the CS behaviors of these dyads were obtained, such as the solvent effects on free energy and the B-length-dependent electronic coupling (VDA) between D and A. We observed the sharp switch of the CS behavior with the increase of the solvent polarity and B-linker lengths. Furthermore, in the case of the shortest distance between D and A when the electron coupling is sufficiently large, we observed that the CS phenomenon occurs even in low-polar solvents. Upon increasing the length of B, CS occurs only in strong polar solvents. The distance-dependent decay constant of the CS rate is determined as ∼0.53 Å-1, indicating that CS is governed by superexchange tunneling interactions. The CS rate constants are also approximately estimated using Marcus electron transfer theory, and the results imply that the VDA value is the key factor dominating the CS rate, while the facile rotation of the phenylene B is important for modulating the lifetime of the charge-separated state in these D-B-A dyads. These results shed light on the practical strategy for obtaining a high CS efficiency with a long-lived CS state in TAA-B-Pyr derivatives.

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.

Electrical Loss Management by Molecularly Manipulating Dopant-free Poly(3-hexylthiophene) towards 16.93 % CsPbI2 Br Solar Cells.

Inorganic cesium lead halide perovskites offer a pathway towards thermally stable photovoltaics. However, moisture-induced phase degradation restricts the application of hole transport layers (HTLs) with hygroscopic dopants. Dopant-free HTLs fail to realize efficient photovoltaics due to severe electrical loss. Herein, we developed an electrical loss management strategy by manipulating poly(3-hexylthiophene) with a small molecule, i.e., SMe-TATPyr. The developed P3HT/SMe-TATPyr HTL shows a three-time increase of carrier mobility owing to breaking the long-range ordering of "edge-on" P3HT and inducing the formation of "face-on" clusters, over 50 % decrease of the perovskite surface defect density, and a reduced voltage loss at the perovskite/HTL interface because of favorable energy level alignment. The CsPbI2 Br perovskite solar cell demonstrates a record-high efficiency of 16.93 % for dopant-free HTL, and superior moisture and thermal stability by maintaining 96 % efficiency at low-humidity condition (10-25 % R. H.) for 1500 hours and over 95 % efficiency after annealing at 85 °C for 1000 hours.

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.

Synthesis and electronic coupling studies of cyclometalated diruthenium complexes bridged by 3,3',5,5'-tetrakis(benzimidazol-2-yl)-biphenyl.

Three cyclometalated diruthenium complexes bridged by 3,3',5,5'-tetrakis(benzimidazol-2-yl)biphenyl (H-tbibp) and capped with different terminal ligands have been synthesized and examined. In addition, two monoruthenium complexes with H-tbibp have been prepared for the purpose of comparison studies. The degree of Ru-Ru electronic coupling of these diruthenium complexes has been investigated by electrochemical and intervalence charge-transfer (IVCT) analyses. These results suggest that when the same or similar terminal ligands are used, the strength of H-tbibp in mediating the Ru-Ru coupling is enhanced with respect to that of the previously reported bridging ligand 3,3',5,5'-tetrakis(N-methylbenzimidazol-2-yl)biphenyl, but it is slightly inferior to that of the classical bridging ligand 3,3',5,5'-tetrakis(pyrid-2-yl)biphenyl. This trend is also supported by CNS analyses based on the hole-superexchange mechanism. In addition, DFT calculations have been performed to probe the spin density distributions of the singly-oxidized diruthenium complexes with H-tbibp and TDDFT calculations are used to reproduce the IVCT transitions.

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.

Ratiometric detection of amyloid-ß aggregation by a dual-emissive tris-heteroleptic ruthenium complex.

A dual-emissive tris-heteroleptic ruthenium complex is designed, synthesized and applied for the ratiometric photoluminescent detection of amyloid-ß (Aß) aggregation in both steady and transient states. The Aß aggregation is supported by transmission electron microscopy and confocal laser scanning microscopy analysis. In addition, molecular docking calculations have been performed to gain insights into the interaction mode between the ruthenium complex and Aß fibrils.

Introducing fluorene into organic hole transport materials to improve mobility and photovoltage for perovskite solar cells.

A new small molecular hole-transporting material, 1,3,6,8-tetrakis[N-(p-methoxyphenyl)-N'-(9,9'-dimethyl-9H-fluoren-2-yl)-amino]pyrene (TFAP) was synthesized and applied in CH3NH3PbI3-perovskite solar cells. A best power conversion efficiency of 19.7% with a photovoltage of 1.11 V has been achieved.

Electrochromism in Electropolymerized Films of Pyrene-Triphenylamine Derivatives.

Two star-shaped multi-triphenylamine derivatives 1 and 2 were prepared, where 2 has an additional phenyl unit between a pyrene core and surrounding triphenylamine units. The oxidative electropolymerization of 1 and 2 occurred smoothly to give thin films of polymers P1 and P2. The electrochemistry and spectroelectrochemistry of P1 and P2 were examined, showing two-step absorption spectral changes in the near-infrared region. The electrochromic properties, including contrast ratio, response time, and cyclic stability of P1 and P2 were investigated and compared. Thin film of P2 displays slightly better electrochromic performance than P1, with a contrast ratio of 45% at 1475 nm being achieved.

Stabilization of a Cyclometalated Ruthenium Sensitizer on Nanocrystalline TiO2 by an Electrodeposited Covalent Layer.

A cyclometalated ruthenium sensitizer 3 containing a triphenylamine unit was synthesized and immobilized on a nanocrystalline TiO2 surface. By using oxidative electrochemical deposition, a covalent layer of a related cyclometalated ruthenium complex 2 was coupled to the top of dye 3. Electrochemical studies suggested that complex 2 was immobilized on the TiO2/3 film surface by a tetraphenylbenzidine linker to form a dimer-like structure. The immobilization of 3 and 2 was further supported by absorption spectral analysis. The resulting electrodeposited TiO2/(3+2) film displays significantly enhanced sensitizer stabilization toward basic aqueous NaOH solution with respect to the original TiO2/3 film. The dye-sensitized solar cells with the TiO2/(3+2) photoanode display a power conversion efficiency of 4.4%, which is slightly inferior to that with the TiO2/3 film (5.1%) under the same measurement conditions.

Nanocrystalline Sb-doped SnO2 films modified with cyclometalated ruthenium complexes for two-step electrochromism.

Sb-Doped nanocrystalline SnO2 (SnO2:Sb) thin films functionalized with cyclometalated ruthenium complexes 1 or 2 on FTO conductive glasses have been prepared and characterized. These complexes contain a redox-active amine unit separated from the ruthenium ion by a phenyl or biphenyl linker, respectively, to modify the absorption wavelengths at different redox states. Near-infrared electrochromism of both films has been examined by oxidative spectroelectrochemical measurements and double-potential-step chronoamperometry. A contrast ratio (ΔT%) of 33% at 1070 nm and 63% at 696 nm has been achieved for the SnO2:Sb/1 film in two stepwise oxidation processes, respectively. The other film with complex 2 shows two-step electrochromism at 1310 and 806 nm with ΔT% of 36% and 76%, respectively. The response time of electrochromic switching is around a few seconds. Taking advantage of the good contrast ratio, the rapid response, and the long retention time of each oxidation state, these films have been successfully used to demonstrate surface-confined flip-flop memory functions with a high ON/OFF ratio.

Molecular Quadripod as a Noncovalent Interfacial Coupling Reagent for Forming Immobilized Coordination Assemblies.

A pyrene-cored molecular quadripod 1,3,6,8-tetra(di( p-pyrid-4-ylphenyl)amino)pyrene (TAPyr) is presented as a noncovalent interfacial coupling reagent for the immobilization of coordination assemblies. This bench-stable molecule is readily available and has a quadripod shape with four pyridine legs and four pyridine handles on the top exterior. By a simple and short dipping procedure under ambient conditions, TAPyr is firmly immobilized on electrode surfaces in an upright fashion as probed by electrochemical, absorption spectral, atomic force microscopy, and scanning tunneling microscopy analysis. Using Pd(PhCN)2Cl2 as a metallolinker, 4-ferrocenylpyridine, a pyridine-terminated monoruthenium complex 1, and a diruthenium complex 2 with two pyridine ends have been grafted onto the ITO/TAPyr surface. The obtained thin films exhibit good electrochemical stability that is comparable or superior to those prepared by the state-of-the-art Si-O-Sn covalent functionalization. Appealing electrochromism is demonstrated with the thin films of ruthenium complexes on ITO.