Extensively Reversible Thermal Transformations of a Bistable,Fluorescence‐Switchable Molecular Solid: Entry into Functional Molecular Phase‐Change Materials

Functional phase‐change materials (PCMs) are conspicuously absent among molecular materials in which the various attributes of inorganic solids have been realized. While organic PCMs are primarily limited to thermal storage systems, the amorphous–crystalline transformation of materials like Ge‐Sb‐Te find use in advanced applications such as information storage. Reversible amorphous–crystalline transformations in molecular solids require a subtle balance between robust supramolecular assembly and flexible structural elements. We report novel diaminodicyanoquinodimethanes that achieve this transformation by interlinked helical assemblies coupled with conformationally flexible alkoxyalkyl chains. They exhibit highly reversible thermal transformations between bistable (crystalline/amorphous) forms, along with a prominent switching of the fluorescence emission energy and intensity.     

聚乙二醇/二醋酸纤维素相变材料的组成与储能性能间的关系

以刚性的二醋酸纤维素 (CDA)链为骨架 ,接枝上聚乙二醇 (PEG)柔性链段 ,可得到一种具有固固相变性能的网状储能材料 .利用该材料的PEG支链从结晶态到无定形态间的相转变 ,可以实现储能和释能的目的 .具体研究了PEG的百分含量及PEG的分子量对材料储能性能的影响 .研究结果表明 ,通过改变PEG的百分含量与PEG的分子量 ,可以得到不同相变焓和不同相变温度的材料     

polyMOFs: A Class of Interconvertible Polymer‐Metal‐Organic‐Framework Hybrid Materials

Preparation of porous materials from one‐dimensional polymers is challenging because the packing of polymer chains results in a dense, non‐porous arrangement. Herein, we demonstrate the remarkable adaptation of an amorphous, linear, non‐porous, flexible organic polymer into a three‐dimensional, highly porous, crystalline solid, as the organic component of a metal–organic framework (MOF). A polymer with aromatic dicarboxylic acids in the backbone functioned as a polymer ligand upon annealing with Zn^II, generating a polymer–metal–organic framework (polyMOF). These materials break the dogma that MOFs must be prepared from small, rigid ligands. Similarly, polyMOFs contradict conventional polymer chemistry by demonstrating that linear and amorphous polymers can be readily coaxed into a highly crystalline, porous, three‐dimensional structure by coordination chemistry.     

Mechanochromic Luminescence of Fluorenyl‐Substituted Ethylenes

It has been reported several times that some organic luminogens with aggregation‐induced emission (AIE) characteristics exhibit the abnormal phenomenon of crystallization‐induced blueshift fluorescence, which makes them suitable for utilization as luminescence color‐switching materials. Because of the attractive application potential and the numerous underlying structure–property relationships in such materials, we investigated a series of fluorenyl‐containing tetrasubstituted ethylenes for their novel optical properties and structural features. The dyes show morphology‐dependent luminescence. Their emission color can be switched between green and blue by means of mechanical grinding and solvent fuming. The transformation between crystalline and amorphous accounts for the luminescence changing. Through single‐crystal and X‐ray diffraction (XRD) analysis, the twisted molecular geometries and loose packing motifs in the crystalline samples are believed to be the intrinsic origin of the external‐stimuli‐induced structural transformation.     

Homogeneous-to-Heterogeneous-Strategy Enables Multifunctional Phase-Change Materials for Energy Storage

Functional phase-change materials (PCMs) are conspicuously absent in various organic or inorganic solids with diversified applications in which the attributes of these molecular materials have been highly realized. Leakage problem during the phase transition process is the main obstacle on the way of widely use of solid-liquid PCMs who has been recognized to be promisingly practical candidates for energy storage owing to the high energy storage density and small volume change in the phase transition process. Herein, a novel homogeneous-to-heterogeneous-strategy, in which all the starting materials involved display a homogeneous state and the encapsulation framework formed in situ in the encapsulation process, enabled by an aerogel reaction of silica was realized under the catalysis of an organic base. Besides the comprehensive study upon energy storage performance, light-to-thermal conversion and recyclability performance study of the obtained materials reveal the clear superiority over pristine paraffin wax (PW) thanks to the versatility and robustness of this fabrication method. More importantly, the homogeneous-to-heterogeneous-strategy endows a unique adsorption ability with respect to organic pollutant due to the PCMs inside and therefore bearing a great potential to be used in environment protection fields.     

Switchable Dielectric Phase Transition Triggered by Pendulum‐Like Motion in an Ionic Co‐crystal

Molecular‐based ionic co‐crystals, which have the merits of low‐cost/easy fabrication processes and flexible structure and functionality, have already exhibited tremendous potential in molecular memory switches and other electric devices. However, dipole (ON/OFF switching) triggering is a huge challenge. Here, we introduce a pendulum‐like dynamic strategy to induce the order–disorder transition of a co‐crystal [C₅H₇N₃Cl]₃[Sb₂Br₉] (compound 1 ). Here, the anion and cation act as a stator and a pendulum‐like rotor (the source of the dielectric switch), respectively. The temperature‐dependent dielectric and differential scanning calorimetry (DSC) analyses reveal that 1 undergoes a reversible phase transition, which stems from the order–disorder transition of the cations. The thermal ON/OFF switchable motions make 1 a promising candidate to promote the development of bulk crystals as artificial intelligent dielectric materials. In addition, the pendulum‐like molecular dynamics and distinct arrangements of two coexisting ions with a notable offset effect promotes/hinders dipolar reorientation after dielectric transition and provides a rarely observed but fairly useful and feasible strategy for understanding and modulating the dipole motion in crystalline electrically polarizable materials.     

In Situ Microscopic Observation of the Crystallization Process of Molecular Microparticles by Fluorescence Switching

To clearly understand the solid‐state amorphous‐to‐crystalline transformation is a long‐standing challenge because such crystallization occuring in confined environments is difficult to observe directly. We developed an in situ and real‐time imaging procedure to record the interface evolution in a solid‐state crystallization of molecular amorphous particles. The method, by employing a tetra‐substituted ethene with novel morphology‐dependent fluorescence, which can distinguish the interfaces between the crystalline and amorphous phase by fluorescence color, is a simple and practical method to probe the inner process of a molecular microparticle. The crystallization of amorphous microparticles in different cases was clearly recorded, where the perfect microparticles and those with defects demonstrate diverse destinies. The details disclosed in this observation will deepen the understanding for a series of solid‐state crystallization that we know little about before.     

Emerging Applications of Phase‐Change Materials (PCMs): Teaching an Old Dog New Tricks

The nebulous term phase‐change material (PCM) simply refers to any substance that has a large heat of fusion and a sharp melting point. PCMs have been used for many years in commercial applications, mainly for heat management purposes. However, these fascinating materials have recently been rediscovered and applied to a broad range of technologies, such as smart drug delivery, information storage, barcoding, and detection. With the hope of kindling interest in this incredibly versatile range of materials, this Review presents an array of aspects related to the compositions, preparations, and emerging applications of PCMs.     

A Molecular Approach to Self‐Supported Cobalt‐Substituted ZnO Materials as Remarkably Stable Electrocatalysts for Water Oxidation

In regard to earth‐abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt‐substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low‐temperature solvolysis of molecular heterobimetallic Co_4?xZn_xO₄ (x=1–3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self‐supported water‐oxidation electrocatalyst, which was observed by HR‐TEM on FIB lamellas of the EPD layers. The Co‐rich hydroxide‐oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours.     

Micro‐/Nanostructured Multicomponent Molecular Materials: Design,Assembly, and Functionality

Molecule‐based micro‐/nanomaterials have attracted considerable attention because their properties can vary greatly from the corresponding macro‐sized bulk systems. Recently, the construction of multicomponent molecular solids based on crystal engineering principles has emerged as a promising alternative way to develop micro‐/nanomaterials. Unlike single‐component materials, the resulting multicomponent systems offer the advantages of tunable composition, and adjustable molecular arrangement, and intermolecular interactions within their solid states. The study of these materials also supplies insight into how the crystal structure, molecular components, and micro‐/nanoscale effects can influence the performance of molecular materials. In this review, we describe recent advances and current directions in the assembly and applications of crystalline multicomponent micro‐/nanostructures. Firstly, the design strategies for multicomponent systems based on molecular recognition and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low‐dimensional multicomponent micro‐/nanostructures. Their new applications are also outlined. Finally, we briefly discuss perspectives for the further development of these molecular crystalline micro‐/nanomaterials.     

Polymeric micro‐sequential concentric transcrystalline morphology self‐assembly,with intermittent self‐shear‐oriented amorphous layers

The investigation and understanding of polymer crystallization processes, the resulting crystalline morphologies, and the mechanism of their formation is crucial in creating materials with desired properties for specific applications. The present research introduces and investigates a new polymeric crystalline morphology, observed for the first time in this research. This newly observed morphology, is a sequentially micro‐multi‐layered concentric morphology that self‐assembles throughout the bulk polymer matrix, with intermittent self‐shear‐oriented amorphous layers. The research analyses the structure and mechanism of its formation. Polarized light microscopy studies have shown a drastic and sudden morphology change that occurred during crystalline growth. Crystalline‐growth kinetics studies performed, showed a distinct pulsatile repeating growth pattern of approximately two growth pulses per second. Thermal analysis indicated the presence of two different populations of crystalline strength. Crystalline structure was analyzed by XRD pattern measurements. It was demonstrated here, that the sequential concentric transcrystalline morphology is nucleated on a shear‐oriented amorphous molecular layer in the adjacent melt formed during and as a consequence of crystalline growth, which occurs in a micro‐periodic sequences, with intermittent self‐sheared amorphous layers. The structure was confirmed by both scanning electron microscope and reflectance microscopy. Small angle X‐ray scattering measurements of the same materials reported in literature are consistent with the melt shear‐orientation theory described earlier. The discovery of this new crystalline morphology in this research, potentially opens a new door in the vast field of material properties and applications. Copyright © 2017 John Wiley & Sons, Ltd.     

Crystallization kinetics of tellurium-rich Se–Te–Sn glassy alloys

The objective of this study was to explore an innovative type of form-stable phase-change materials (PCMs) with flexible cellulose acetate (CA) nano-fibrous felts (nano-felts) absorbed with capric–myristic–stearic acid ternary eutectic mixture for thermal energy storage/retrieval. Capric–myristic–stearic acid (CMS) ternary eutectic mixture as model PCM was firstly prepared. The developed CA nano-felts as supporting material was mechanically flexible and was made from CA/polyvinylpyrrolidone (PVP) precursor composite nanofibers followed by removal of PVP components. The effects of original mass ratio of CA/PVP on absorption capacities of CA nano-felts were studied. The modified CA nano-felts with groove/porous structure and rough surfaces were capable of absorbing a large amount of PCMs. The morphological structures, as well as the properties of thermal energy storage, thermal stability and reliability, and thermal insulation of composite PCMs were characterized by scanning electron microscopy, differential scanning calorimetry, and thermal performance measurement, respectively. The results showed that CMS eutectic was absorbed in and/or supported by modified CA nano-felts. The heat enthalpy values of composite PCMs have slightly decreased in comparison with the corresponding theoretical values. The composite PCMs demonstrated good thermal stability and reliability after thermal cycles. The composite PCMs had high thermal insulation capability for temperature regulation.     

Modulating Photo‐ and Electroluminescence in a Stimuli‐Responsive π‐Conjugated Donor–Acceptor Molecular System

Functional organic materials that display reversible changes in fluorescence in response to external stimuli are of immense interest owing to their potential applications in sensors, probes, and security links. While earlier studies mainly focused on changes in photoluminescence (PL) color in response to external stimuli, stimuli‐responsive electroluminescence (EL) has not yet been explored for color‐tunable emitters in organic light‐emitting diodes (OLEDs). Here a stimuli‐responsive fluorophoric molecular system is reported that is capable of switching its emission color between green and orange in the solid state upon grinding, heating, and exposure to chemical vapor. A mechanistic study combining X‐ray diffraction analysis and quantum chemical calculations reveals that the tunable green/orange emissions originate from the fluorophore's alternating excited‐state conformers formed in the crystalline and amorphous phases. By taking advantage of this stimuli‐responsive fluorescence behavior, two‐color emissive OLEDs were produced using the same fluorophore in different solid phases.     

Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

Molecular solar‐thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193–260 g mol^?1) norbornadiene–quadricyclane systems. The molecules feature cyano acceptor and ethynyl‐substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo‐thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396–629 kJ kg^?1). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules.     

Advances in Photonic Devices Based on Optical Phase-Change Materials

Phase-change materials (PCMs) are important photonic materials that have the advantages of a rapid and reversible phase change, a great difference in the optical properties between the crystalline and amorphous states, scalability, and nonvolatility. With the constant development in the PCM platform and integration of multiple material platforms, more and more reconfigurable photonic devices and their dynamic regulation have been theoretically proposed and experimentally demonstrated, showing the great potential of PCMs in integrated photonic chips. Here, we review the recent developments in PCMs and discuss their potential for photonic devices. A universal overview of the mechanism of the phase transition and models of PCMs is presented. PCMs have injected new life into on-chip photonic integrated circuits, which generally contain an optical switch, an optical logical gate, and an optical modulator. Photonic neural networks based on PCMs are another interesting application of PCMs. Finally, the future development prospects and problems that need to be solved are discussed. PCMs are likely to have wide applications in future intelligent photonic systems.     

Molecular Engineering for Metal‐Free Amorphous Materials with Room‐Temperature Phosphorescence

Materials displaying room‐temperature phosphorescence (RTP) have been attracting wide attention in recent years due to their distinctive characteristics including long emissive lifetime and large Stokes shift, and their various applications. Most synthesized RTP materials are metal complexes that display enhanced intersystem crossing and crystallization is a common way to restrict nonradiative transition. Amorphous metal‐free RTP materials, which do not rely on expensive and toxic metals and can be prepared in a straightforward fashion, have become an important branch of the field. This Minireview summarizes recent progress in amorphous RTP materials according to the approaches used to immobilize phosphors: host–guest interactions, molecule doping, copolymers, and small‐molecule self‐assembly. Some existing challenges and insightful perspectives are given at the end of the Minireview, which should benefit the future design and development of amorphous metal‐free RTP materials.     

Fluorescence Emission from 2,6‐Naphthylene‐Bridged Mesoporous Organosilicas with an Amorphous or Crystal‐Like Framework

We report that 2,6‐naphthylene‐bridged periodic mesoporous organosilicas exhibit unique fluorescence behavior that reflects molecular‐scale periodicities in the framework. Periodic mesoporous organosilicas consisting of naphthalene–silica hybrid frameworks were synthesized by hydrolysis and condensation of a naphthalene‐derived organosilane precursor in the presence of a template surfactant. The morphologies and meso‐ and molecular‐scale periodicities of the organosilica materials strongly depend on the synthetic conditions. The naphthalene moieties embedded within the molecularly ordered framework exhibited a monomer‐band emission, whereas those embedded within the amorphous framework showed a broad emission attributed to an excimer band. These results suggest that the naphthalene moieties fixed within the crystal‐like framework are isolated in spite of their densely packed structure, different from conventional organosilica frameworks in which only excimer emission was observed for both the crystal‐like and amorphous frameworks at room temperature. This key finding suggests a potential to control interactions between organic groups and thus the optical properties of inorganic/organic hybrids.     

Molecular Spring‐like Triple‐Helix Coordination Polymers as Dual‐Stress and Thermally Responsive Crystalline Metal–Organic Materials

Elastic metal–organic materials (MOMs) capable of multiple stimuli‐responsiveness based on dual‐stress and thermally responsive triple‐helix coordination polymers are presented. The strong metal‐coordination linkage and the flexibility of organic linkers in these MOMs, rather than the 4 Å stacking interactions observed in organic crystals, causes the helical chain to act like a molecular spring and thus accounts for their macroscopic elasticity. The thermosalient effect of elastic MOMs is reported for the first time. Crystal structure analyses at different temperatures reveal that this thermoresponsiveness is achieved by adaptive regulation of the triple‐helix chains by fine‐tuning the opening angle of flexible V‐shaped organic linkers and rotation of its lateral conjugated groups to resist possible expansion, thus demonstrating the vital role of adaptive reorganization of triple‐helix metal–organic chains as a molecular spring‐like motif in crystal jumping.     

2D Oligosilyl Metal–Organic Frameworks as Multi‐state Switchable Materials

We report the synthesis of a set of 2D metal–organic frameworks (MOFs) constructed with organosilicon‐based linkers. These oligosilyl MOFs feature linear Si_nMe_2n(C₆H₄CO₂H)₂ ligands (lin‐Si_n, n=2, 4) connected by Cu paddlewheels. The stacking arrangement of the 2D sheets is dictated by van der Waals interactions and is tunable by solvent exchange, leading to reversible structural transformations between many crystalline and amorphous phases.     

Crystallization of a Two‐Dimensional Hydrogen‐Bonded Molecular Assembly: Evolution of the Local Structure Resolved by Atomic Force Microscopy

Structures of the aromatic N‐heterocyclic hexaazatriphenylene (HAT) molecular synthon obtained by surface‐assisted self‐assembly were analyzed with sub‐Å resolution by means of noncontact atomic force microscopy (nc‐AFM), both in the kinetically trapped amorphous state and in the thermodynamically stable crystalline phase. These results reveal how the crystallization governs the length scale of the network order for non‐flexible molecular species without affecting the local bonding schemes. The capability of nc‐AFM to accurately resolve structural relaxations will be highly relevant for the characterization of vitreous two‐dimensional supramolecular materials.