Endowing single-crystal polymers with circularly polarized luminescence.

The preparation of single-crystal polymers with circularly polarized luminesce (CPL) remains a challenging task in chemistry and materials science. Herein, we present the single-crystal-to-single-crystal topochemical photopolymerization of a chiral organic salt to achieve this goal. The in-situ reaction of 1,4-bis((E)-2-(pyridin-4-yl)vinyl)benzene (1) with chiral (+)- or (-)-camphorsulfonic acid (CSA) gives the monomer crystal 1[( + )/( - )-CSA] showing yellow CPL with a high luminescent dissymmetry factor |g| of 0.

Self-Healing 2D Anion-Organic Frameworks for Low-Temperature Water Release.

Molecular frameworks have recently shown a great potential in atmospheric water harvesting, in which the water release at low temperatures is challenging. Anion-organic frameworks based on anion-coordination chemistry are presented herein to meet this challenge. These frameworks are prepared as tubular single crystals in pure water from the in situ protonation and crystallization of pyridine-terminated triphenylamine derivatives with hydrochloric or hydrobromic acid.

An organic polarized photonic heterostructure based on tetra(4-pyridylphenyl)ethylene.

Organic optical heterostructures have emerged as promising candidates for applications in organic photonics. In this study, we demonstrate a facile strategy to integrate different emission and polarization properties into the sub-blocks of luminescent organic heterostructures, by a mask-assisted vapor treatment method on the microcrystals of a pyridine-functionalized tetraphenylethylene chromophore.

Tuning the circularly polarized phosphorescence of platinum(II) complexes through a chiral cation strategy.

Circularly polarized phosphorescent (CPP) materials, especially chiral platinum(II) complexes, which combine the advantages of both circularly polarized luminescence (CPL) and phosphorescence, show broad potential applications in chiral optoelectronic devices. Developing CPP emitters with both excellent chiroptical properties and high yield is urgently needed. Here, a chiral cation strategy is employed to construct the CPP Pt(II) complexes /-ABA·[Pt(ppy)Cl] and /-MBA·[Pt(ppy)Cl] through a simple one-step reaction with almost 100% yield.

Ratiometric Imaging Detection of Amyloid-β Fibrils by a Dual-Emissive Tris-Heteroleptic Ruthenium Complex.

Two dual fluorescent/phosphorescent tris-heteroleptic mononuclear Ru(ΙΙ) complexes ( and ) were designed and applied in amyloid-β (Aβ) sensing. These complexes have a general formula of [Ru(phen)(dppz)()](PF), where is (2-pyrazinyl)(2-pyridyl)(methyl)amine (H-) with different substituents (-OMe for , -H for ), phen is 1,10-phenanthroline, and dppz is dipyridophenazine, respectively. Compared with the previously reported ratiometric probe with a di(pyrid-2-yl)(methyl)amine ligand, complex can be employed for not only ratiometric emissive detection of Aβ aggregation but also ratiometric imaging detection of Aβ fibrils.

Triphenylamine-Based Covalent Organic Framework Films for Dopamine-Responsive Electrofluorochromism.

Covalent organic framework (COF) film with electrofluorochromic (EFC) and electrochromic (EC) properties has been synthesized by using triphenylamine-based monomers. The film exhibited a high maximum fluorescence contrast of 151 when subjected to a drive voltage of 0.75 V vs the Ag/AgCl electrode, causing the fluorescence to be quenched, which resulted in the EFC process's "fluorescence off" state.

Multicolor Electrochemiluminescence of Binary Microcrystals of Iridium and Ruthenium Complexes.

We here report the multicolor electrochemiluminescence (ECL) of binary microcrystals prepared from a blue-emissive iridium complex 1 and an orange-emissive ruthenium complex 2. These materials display a plate-like morphology with high crystallinity, as demonstrated by microscopic and powder X-ray diffraction analyses. Under light excitation, these microcrystals exhibit gradient emission color changes as a result of the efficient energy transfer between two complexes.

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 with 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.

Divergent Synthesis of Enantioenriched Silicon-Stereogenic Benzyl-, Vinyl- and Borylsilanes via Asymmetric Aryl to Alkyl 1,5-Palladium Migration.

Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction of silicon-stereogenic architectures by functionalization of Si-bound methyl group has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed the enantioselective silylmethyl functionalization involving the aryl to alkyl 1,5-palladium migration to access diverse naphthalenes possessing an enantioenriched stereogenic silicon center, which are inaccessible before.

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.

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 (g) 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.

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 TiO 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/cm has been achieved with O and H 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.

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.

A 3D nanoscale optical disk memory with petabit capacity.

High-capacity storage technologies are needed to meet our ever-growing data demands. However, data centres based on major storage technologies such as semiconductor flash devices and hard disk drives have high energy burdens, high operation costs and short lifespans. Optical data storage (ODS) presents a promising solution for cost-effective long-term archival data storage.

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

Three monoruthenium complexes (PF)-(PF) bearing an N(CH)-bridged ligand have been synthesized and characterized. These complexes have a general formula of [Ru(bpy)()](PF), where is a 2,5-di(-methyl-'-(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.

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.

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

TiO 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 H generation with a production rate of around 250 μmol h is realized with a photoanode of an active area of 5 × 5 cm.

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 Ir and Ru 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 ), in stark contrast to the very weak circularly polarized photoluminescence of the spin-coated films of these diastereomeric complexes.

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.

Molecular Cocrystals with Hydrogen-Bonded Polymeric Structures and Polarized Luminescence.

Crystalline materials with appealing luminescent properties are attractive materials for various optoelectronic applications. The in situ bicomponent reaction of 1,2-ethylenedisulfonic acid with 1,4-di(pyrid-2-yl)benzene, 1,4-di(pyrid-3-yl)benzene, or 1,4-di(pyrid-4-yl)benzene affords luminescent crystals with hydrogen-bonded polymeric structures. Variations in the positions of the pyridine nitrogen atoms lead to alternating polymeric structures with either a ladder- or zigzag-type of molecular arrangement.

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.

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.

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 () between D and A.