A Mechanochemically Triggered “Click” Catalyst

“Click” chemistry represents one of the most powerful approaches for linking molecules in chemistry and materials science. Triggering this reaction by mechanical force would enable site‐ and stress‐specific “click” reactions—a hitherto unreported observation. We introduce the design and realization of a homogeneous Cu catalyst able to activate through mechanical force when attached to suitable polymer chains, acting as a lever to transmit the force to the central catalytic system. Activation of the subsequent copper‐catalyzed “click” reaction (CuAAC) is achieved either by ultrasonication or mechanical pressing of a polymeric material, using a fluorogenic dye to detect the activation of the catalyst. Based on an N‐heterocyclic copper(I) carbene with attached polymeric chains of different flexibility, the force is transmitted to the central catalyst, thereby activating a CuAAC in solution and in the solid state.     

Multistimuli‐Responsive Luminescence Switching of Pyrazine Derivative Based Donor–Acceptor–Donor Luminophores

Three symmetrical donor–acceptor–donor (D–A–D) luminophores ( C1 , C2 , and C3 ) with pyrazine derivatives as electron‐withdrawing groups have been developed for multistimuli‐responsive luminescence switching. For comparison, reference compounds R1 and R2 without the pyrazine moiety have also been synthesized. Intramolecular charge transfer (ICT) interactions can be found for all D–A–D luminophores owing to the electron‐withdrawing properties of the two imine nitrogen atoms in the pyrazine ring and the electron‐donating properties of the other two amine nitrogen atoms in the two triphenylamine units. Moreover, luminophores C1 , C2 , and C3 exhibit “on–off–on” luminescence switching properties in mixtures of water/tetrahydrofuran with increasing water content, which is different from the “on–off” switching for typical aggregation‐caused quenching (ACQ) materials and “off–on” switching for traditional aggregation‐induced emission (AIE) materials. Additionally, upon grinding the pristine samples, luminophores C1 , C2 , and C3 display bathochromically shifted photoluminescence maxima that can be recovered by either solvent fuming or thermal annealing treatments. The piezofluorochromic (PFC) properties are more pronounced than those for reference compounds R1 and R2 , which indicates that D–A molecules have the ability to amplify the PFC effect by tuning the ICT interactions upon tiny structural changes under pressure. Furthermore, the target luminophores demonstrate acid‐responsive photoluminescence spectra that can be recovered in either basic or ambient environments. These results suggest that D–A complexes are potential candidates for multistimuli‐responsive luminescence switching because their ICT profiles can be facilely tuned with tiny external stimuli.     

Bright White‐Light Emission from a Single Organic Compound in the Solid State

White‐light‐emitting materials and devices have attracted enormous interest because of their great potential for various lighting applications. We herein describe the light‐emitting properties of a series of new difunctional organic molecules of remarkably simple structure consisting of two terminal 4‐pyridone push–pull subunits separated by a polymethylene chain. They were found to emit almost “pure” white light as a single organic compound in the solid state, as well as when incorporated in a polymer film. To the best of our knowledge, they are the simplest white‐light‐emitting organic molecules reported to date.     

Scanning‐Tunneling‐Spectroscopy‐Directed Design of Tailored Deep‐Blue Emitters

Frontier molecular orbitals can be visualized and selectively set to achieve blue phosphorescent metal complexes. For this purpose, the HOMOs and LUMOs of tridentate Pt^II complexes were measured using scanning tunneling microscopy and spectroscopy. The introduction of electron‐accepting or ‐donating moieties enables independent tuning of the frontier orbital energies, and the measured HOMO–LUMO gaps are reproduced by DFT calculations. The energy gaps correlate with the measured and the calculated energies of the emissive triplet states and the experimental luminescence wavelengths. This synergetic interplay between synthesis, microscopy, and spectroscopy enabled the design and realization of a deep‐blue triplet emitter. Finding and tuning the electronic “set screws” at molecular level constitutes a useful experimental method towards an in‐depth understanding and rational design of optoelectronic materials with tailored excited state energies and defined frontier‐orbital properties.     

Understanding the Unconventional Effects of Halogenation on the Luminescent Properties of Oligo(Phenylene Vinylene) Molecules

It is commonly known that halogenation tends to decrease the luminescence quantum yield of an organic dye, owing to the high electronegativity and heavy‐atom effect of the halogen atom. However, based on an investigation of the effects of halogenation on the luminescence of the oligo(phenylene vinylene) (OPV) framework, we demonstrate that halogenation can have positive impact on the solid‐state fluorescence and electrochemiluminescence (ECL) properties of OPV derivatives. The chlorinated OPV exhibits a very high solid‐state fluorescence quantum yield (91 %), whilst the brominated analogue gives the highest ECL emission intensity. Time‐dependent density functional theory calculations, natural bond orbital analysis, and natural transition orbital analysis were performed to assist the understanding of the origin of these positive halogenation effects, which provide insight into the rational design of highly luminescent halogenated organic materials for solid‐state devices and ECL applications.     

Organic Fluorophores Exhibiting Highly Efficient Photoluminescence in the Solid State

There has been extensive research on the development of organic optoelectronic devices, such as organic light‐emitting diodes, organic field‐effect transistors, and organic solid‐state lasers from various viewpoints, ranging from basic studies to practical applications. As organic materials are used as solids in these devices, the importance of organic chromophores that exhibit intense emissions of visible light in the solid state is greatly increasing in the field of organic electronics. However, highly efficient emission from organic solids is very difficult to attain because most organic emitting materials strongly tend to cause concentration quenching of the luminescence in the condensed phase. Therefore, in order to generate and improve organic optoelectronic devices, it is necessary to design novel chromophores that exhibit superior solid‐state emission performance. This Focus Review covers the recent development of highly emissive organic small molecules whose photoluminescence quantum yields in the solid state have been reported. Following the introduction, the photophysical processes of excited molecules are briefly reviewed. Subsequently, organic solid fluorophores are described with an emphasis on the characteristics of their molecular structures.     

Structural Transformation Pathways of Alkaline Earth Family Coordination Polymers Containing 3,3′,5,5′‐Biphenyl Tetracarboxylic Acid

The understanding of crystal stepwise transformation is very important to enclose the “black box” in the preparation of crystal materials. In this work, different structural intermediates were isolated prior to the formation of the final alkali earth coordination polymers (CPs) during the preparation of three pairs of alkali earth CPs through solvothermal method and convenient oil‐bath reactions. Single crystal X‐ray diffraction analysis demonstrated the structural transformation from a 0 D to 1 D inorganic connectivity for the Ca‐CPs and Sr‐CPs, but a 1 D to 0 D inorganic connectivity for Ba‐CPs, involving the breakage/formation of chemical bonds in the reaction solutions. Further analyses indicated that these two different structural transformation pathways are determined by the deprotonation of organic acid, competitive balance between the inorganic and organic connectivity, and the twist of the linker. FT‐IR spectra, thermogravimetric and luminescence behaviors agree with their structural characteristics.     

Phosphorescence Energy Transfer: Ambient Afterglow Fluorescence from Water‐Processable and Purely Organic Dyes via Delayed Sensitization

Ambient afterglow luminescence from metal‐free organic chromophores would provide a promising alternative to the well‐explored inorganic phosphors. However, the realization of air‐stable and solution‐processable organic afterglow systems with long‐lived triplet or singlet states remains a formidable challenge. In the present study, a delayed sensitization of the singlet state of organic dyes via phosphorescence energy transfer from organic phosphors is proposed as an alternative strategy to realize “afterglow fluorescence”. This concept is demonstrated with a long‐lived phosphor as the energy donor and commercially available fluorescent dyes as the energy acceptor. Triplet‐to‐singlet Förster‐resonance energy‐transfer (TS‐FRET) between donor and acceptor chromophores, which are co‐organized in an amorphous polymer matrix, results in tuneable yellow and red afterglow from the fluorescent acceptors. Moreover, these afterglow fluorescent hybrids are highly solution‐processable and show excellent air‐stability with good quantum yields.     

Highly Efficient Enrichment of Volatile Iodine by Charged Porous Aromatic Frameworks with Three Sorption Sites

The targeted synthesis of a series of novel charged porous aromatic frameworks (PAFs) is reported. The compounds PAF‐23, PAF‐24, and PAF‐25 are built up by a tetrahedral building unit, lithium tetrakis(4‐iodophenyl)borate (LTIPB), and different alkyne monomers as linkers by a Sonogashira–Hagihara coupling reaction. They possess excellent adsorption properties to organic molecules owing to their “breathing” dynamic frameworks. As these PAF materials assemble three effective sorption sites, namely the ion bond, phenyl ring, and triple bond together, they exhibit high affinity and capacity for iodine molecules. To the best of our knowledge, these PAF materials give the highest adsorption values among all porous materials (zeolites, metal–organic frameworks, and porous organic frameworks) reported to date.     

Molecular Polygons Probe the Role of Intramolecular Strain in the Photophysics of π‐Conjugated Chromophores

π‐Conjugated segments, chromophores, are the electronically active units of polymer materials used in organic electronics. To elucidate the effect of the bending of these linear moieties on elementary electronic properties, such as luminescence color and radiative rate, we introduce a series of molecular polygons. The π‐system in these molecules becomes so distorted in bichromophores (digons) that these absorb and emit light of arbitrary polarization: any part of the chain absorbs and emits radiation with equal probability. Bending leads to a cancellation of transition dipole moment (TDM), increasing excited‐state lifetime. Simultaneously, fluorescence shifts to the red as radiative transitions require mixing of the excited state with vibrational modes. However, strain can become so large that excited‐state localization on shorter units of the chain occurs, compensating TDM cancellation. The underlying correlations between shape and photophysics can only be resolved in single molecules.     

Functionalization of Pyrene To Prepare Luminescent Materials—Typical Examples of Synthetic Methodology

Pyrene‐based π‐conjugated materials are considered to be an ideal organic electro‐luminescence material for application in semiconductor devices, such as organic light‐emitting diodes (OLEDs), organic field‐effect transistors (OFETs) and organic photovoltaics (OPVs), and so forth. However, the great drawback of employing pyrene as an organic luminescence material is the formation of excimer emission, which quenches the efficiency at high concentration or in the solid‐state. Thus, in order to obtain highly efficient optical devices, scientists have devoted much effort to tuning the structure of pyrene derivatives in order to realize exploitable properties by employing two strategies, 1) introducing a variety of moieties at the pyrene core, and 2) exploring effective and convenient synthetic strategies to functionalize the pyrene core. Over the past decades, our group has mainly focused on synthetic methodologies for functionalization of the pyrene core; we have found that formylation/acetylation or bromination of pyrene can selectly lead to functionalization at K‐region by Lewis acid catalysis. Herein, this Minireview highlights the direct synthetic approaches (such as formylation, bromination, oxidation, and de‐tert‐butylation reactions, etc.) to functionalize the pyrene in order to advance research on luminescent materials for organic electronic applications. Further, this article demonstrates that the future direction of pyrene chemistry is asymmetric functionalization of pyrene for organic semiconductor applications and highlights some of the classical asymmetric pyrenes, as well as the latest breakthroughs. In addition, the photophysical properties of pyrene‐based molecules are briefly reviewed. To give a current overview of the development of pyrene chemistry, the review selectively covers some of the latest reports and concepts from the period covering late 2011 to the present day.     

Conformational Spin Switching and Spin‐Selective Hydrogenation of a Magnetically Bistable Carbene

The control of the spin states of molecules opens the path to tuning selectivity in chemical reactions and to developing novel magnetically switchable materials. 3‐Methoxy‐9‐fluorenylidene is a carbene that is generated in cryogenic matrices both in its lowest energy singlet and triplet states, and the ratio of these states can be shifted by selective irradiation. The interconversion of the nearly degenerate spin states is induced by a conformational change of the methoxy group: switching the methoxy group into the “up” position results in the singlet state and switching into the “down” position in the triplet state. The spin control via a remote functional group makes this carbene unique for the study of spin‐specific reactions, which is demonstrated for the hydrogenation reaction. Spin switching by switching the conformation of a remote functional group is a novel phenomenon with potential applications in the design of functional materials.     

非金属催化剂在催化环氧化物和CO2合成环状碳酸酯中的研究进展

随着科学技术的进步和工业化的发展,大量化石燃料被消耗,大气中二氧化碳浓度急剧增加,导致温室效应加剧,严重威胁到人类的生存和发展。基于可持续发展的思想,利用储量丰富且廉价的二氧化碳作为 C1资源替代有毒的气体(如一氧化碳和光气等)制备具有广泛应用的环状碳酸酯,不仅满足“绿色化学”的要求,而且符合“原子经济性”的原则。迄今为止,大量用于催化二氧化碳和环氧化物环加成反应合成环状碳酸酯的催化剂,包括均相催化剂(如金属卤化物、有机碱、离子液体和金属配合物),多相催化剂(如金属氧化物、负载型催化剂、有机聚合物、金属有机框架材料和碳材料等)被报道。其中金属催化剂占主导地位,大多表现出优异的催化活性。然而,目前可供开采的金属矿越来越少,大多数金属的回收再利用率较低,重金属污染日趋严重。因此,开发新型、廉价、绿色、高效、循环性和稳定性好的非金属催化剂具有重要意义。
　　本文主要介绍了近3年以来用于催化二氧化碳和环氧化物环加成反应合成环状碳酸酯的非金属催化剂,主要包括有机碱、离子液体、固载型催化剂、有机聚合物和碳材料等。概括了不同种类催化剂的设计思想及其催化反应机理,重点阐述了分子内以及分子间各种功能基团的协同作用对环加成反应的影响。通过比较发现,具有“C–N=C”结构的有机碱活性相对较高,氢键给体和亲核物质都能与有机碱协同作用提高其催化活性;传统离子液体的活性一般不理想,氢键给体如羟基和羧基的引入有利于促进环加成反应,且多阳离子和多氢键给体功能化的离子液体表现出更高的催化活性;负载型催化剂中,载体和活性组分之间的协同作用有利于加速环加成反应的进行,多种功能基团负载和以共价键方式多层固载能更好地提高催化剂稳定性和催化活性;利用非烯烃化合物制得的活性组分位于主链的多孔有机聚合物,催化活性和稳定性大多高于活性组分位于侧链的烯烃聚合物;碳材料催化剂中,引入不饱和的 N物种(如伯胺和吡啶氮),有利于 CO2的吸附和活化,能促进环加成反应。此外,利用密度泛函的方法,计算模拟催化反应过程,能更好地揭示反应机理,并为设计和制备高效的催化剂提供理论指导。
　　该领域目前面临的重要挑战是研发可以同时实现二氧化碳捕获和转化的新型、环保和高效非金属催化剂,终极目标是利用多孔催化材料在常温和常压下直接捕获工业废气中的二氧化碳,并利用捕获的二氧化碳实现环状碳酸酯的连续生产。基于协同催化的设计思想,利用多种基团功能化的策略合成高效吸附和活化二氧化碳以及开环活化环氧化物的非金属催化剂,有望实现上述目标。     

Robust Aqua Material: A Pressure‐Resistant Self‐Assembled Membrane for Water Purification

“Aqua materials” that contain water as their major component and are as robust as conventional plastics are highly desirable. Yet, the ability of such systems to withstand harsh conditions, for example, high pressures typical of industrial applications has not been demonstrated. We show that a hydrogel‐like membrane self‐assembled from an aromatic amphiphile and colloidal Nafion is capable of purifying water from organic molecules, including pharmaceuticals, and heavy metals in a very wide range of concentrations. Remarkably, the membrane can sustain high pressures, retaining its function. The robustness and functionality of the water‐based self‐assembled array advances the idea that aqua materials can be very strong and suitable for demanding industrial applications.     

Lasing from an Organic Micro‐Helix

Organic solid‐state semiconductor lasers are attracting ever‐increasing interest for their potential application in future photonic circuits. Despite the great progress made in recent years, an organic laser from 3D chiral structures has not been achieved. Now, the first example of an organic nano‐laser from the micro‐helix structure of an achiral molecule is presented. Highly regular micro‐helixes with left/right‐handed helicity from a distyrylbenzene derivative (HM‐DSB) were fabricated and characterized under microscope spectrometers. These chiral micro‐helixes exhibit unique photonic properties, including helicity‐dependent circularly polarized luminescence (CPL), periodic optical waveguiding, and length‐dependent amplified spontaneous emission (ASE) behavior. The successful observation of laser behavior from the organic micro‐helix extends our understanding to morphology chirality of organic photonic materials and provides a new design strategy towards chiral photonic circuits.     

基于马鞍形环八四噻吩的复合纳米材料的制备及发光性能

由于环八四噻吩具有独特的"马鞍形"空间结构和光电性质,因此受到越来越多的关注.环八四噻吩(COThs)共有14种同分异构体,其中COTh-1是一类特殊的聚集诱导发光体系,但仅在四氢呋喃等少数有机溶剂中有一定的溶解度,发光强度较弱,限制了这类材料的应用.多孔二氧化硅纳米材料具有比表面积大、孔体积大、粒径可调、生物相容性好...     

Uncovering the Intramolecular Emission and Tuning the Nonlinear Optical Properties of Organic Materials by Cocrystallization

The spectroscopic and photophysical properties of organic materials in the solid‐state are widely accepted as a result of their molecular packing structure and intermolecular interactions, such as J‐ and H‐aggregation, charge‐transfer (CT), excimer and exciplex. However, in this work, we show that Spe‐F₄DIB cocrystals (SFCs) surprisingly retain the energy levels of photoluminescence (PL) states of Spe crystals, despite a significantly altered molecular packing structure after cocrystallization. In comparison, Npe‐F₄DIB cocrystals (NFCs) with new spectroscopic states display different spectra and photophysical behaviors as compared with those of individual component crystals. These may be related to the molecular configuration in crystals, and we propose Spe as an “intramolecular emissive” material, thus providing a new viewpoint on light‐emitting species of organic chromophores. Moreover, the nonlinear optical (NLO) properties of Npe and Spe are firstly demonstrated and modulated by cocrystallization. The established “molecule‐packing‐property” relationship helps to rationally control the optical properties of organic materials through cocrystallization.     

Metastable Self‐Assembly of Theta‐Shaped Colloids and Twinning of Their Crystal Phases

Anisotropic colloids self‐assemble into different crystal structures compared to spherical colloids. Exploring and understanding their self‐assembly behavior could lead to creation of new materials with hierarchical structures through a bottom‐up process. Herein, we report metastable self‐assembly of theta‐shaped SiO₂ colloids interacting with a depletion force in a quasi‐two‐dimensional space and we demonstrate that both a metastable “prone” crystal phase and a stable “standing” crystal phase can be formed, depending on the self‐assembly path. Path selection stems from an interplay between particle–particle interactions and particle–wall interactions. In particular, a twinning of the metastable crystals was observed and two twinning mirror axes were found. A variety of complex twinned crystals were formed by each individual mirror axis or their combinations.     

Investigation on “Excimer” Formation Mechanism of Linear Oligofluorenes‐Functionalized Anthracenes by Using Transient Absorption Spectroscopy

We study the photophysical characters of two oligofluorenes‐functionalized anthracenes molecules with different fluorine‐vinylene (FV) units, which exhibits that “excimer” state appears in the solution after photoexcitation. The dynamic data shows that two mechanisms are responsible for the generation of “excimer”. The fast one is controlled by the arene‐arene interaction between molecules and the slow one is influenced by the diffusion motion of molecules. Increasing the number of FV units may suppress the DM‐dependent “excimer” and enhance the yield of intrinsic fluorescence, which finally improves the fluorescence property of molecules in solution.     

Cluster Linker Approach: Preparation of a Luminescent Porous Framework with NbO Topology by Linking Silver Ions with Gold(I) Clusters

A cluster‐based luminescent porous metal–organic framework has been constructed through a “cluster linker” approach. The luminescent gold(I) cluster, prefunctionalized with pyrazinyl groups, was used as a cluster linker, similar to an organic linker, to connect silver ions in order to form a 3D framework. 1D channels with 1.1 nm diameter were observed in the framework. The cluster with its intrinsic luminescence was incorporated into a porous framework to give a luminescent bifunctional NbO net. This MOF shows solvatochromic behavior, and the interactions between solvent molecules and silver ions inside the channels account for the changes in absorption and emission spectra.