Recent Progress in Azobenzene-Based Supramolecular Materials and Applications

Azobenzene-containing small molecules and polymers are functional photoswitchable molecules to form supramolecular nanomaterials for various applications. Recently, supramolecular nanomaterials have received enormous attention in material science because of their simple bottom-up synthesis approach, understandable mechanisms and structural features, and batch-to-batch reproducibility. Azobenzene is a light-responsive functional moiety in the molecular design of small molecules and polymers and is used to switch the photophysical properties of supramolecular nanomaterials. Herein, we review the latest literature on supramolecular nano- and micro-materials formed from azobenzene-containing small molecules and polymers through the combinatorial effect of weak molecular interactions. Different classes including complex coacervates, host-guest systems, co-assembled, and self-assembled supramolecular materials, where azobenzene is an essential moiety in small molecules, and photophysical properties are discussed. Afterward, azobenzene-containing polymers-based supramolecular photoresponsive materials formed through the host-guest approach, polymerization-induced self-assembly, and post-polymerization assembly techniques are highlighted. In addition to this, the applications of photoswitchable supramolecular materials in pH sensing, and CO₂ capture are presented. In the end, the conclusion and future perspective of azobenzene-based supramolecular materials for molecular assembly design, and applications are given.     

Advances in Organic Near‐Infrared Materials and Emerging Applications

Much progress has been made in the field of research on organic near‐infrared materials for potential applications in photonics, communications, energy, and biophotonics. This account mainly describes our research work on organic near‐infrared materials; in particular, donor‐acceptor small molecules, organometallics, and donor‐acceptor polymers with the bandgaps less than 1.2 eV. The molecular designs, structure‐property relationships, unique near‐infrared absorption, emission and color/wavelength‐changing properties, and some emerging applications are discussed.     

Organic Thermoelectric Materials as the Waste Heat Remedy

The primary reason behind the search for novel organic materials for application in thermoelectric devices is the toxicity of inorganic substances and the difficulties associated with their processing for the production of thin, flexible layers. When Thomas Seebeck described a new phenomenon in Berlin in 1820, nobody could have predicted the future applications of the thermoelectric effect. Now, thermoelectric generators (TEGs) are used in watches, and thermoelectric coolers (TECs) are applied in cars, computers, and various laboratory equipment. Nevertheless, the future of thermoelectric materials lies in organic compounds. This paper discusses the developments made in thermoelectric materials, including small molecules, polymers, molecular junctions, and their applications as TEGs and/or TECs.     

裁剪型有机光伏小分子及其衍生物的研究与应用#

有机太阳能电池光电转化效率已经突破13%,这主要归因于活性层材料的不断丰富与改进。其中,以聚合物为母体的裁剪型分子,其相比于聚合物具有明确的分子量,共轭长度可调,高消光系数,优良的结晶性等优势。本文简要介绍裁剪型分子在二元本体异质结体系,三元体系,非富勒烯体系中的应用及我们组的相关研究工作,总结了其特点并对其应用前景做了展望。     

刺激响应纳米碳杂化材料

碳纳米管和石墨烯是碳纳米材料的典型代表,其纳米尺度赋予了其优异的光、电、热以及机械性能。然而,这些碳纳米材料间存在较强的范德华力,导致其溶解性差,后续加工处理困难。为提高碳纳米材料的溶解性,通常利用聚合物或其它小分子物质对其进行修饰。而利用刺激响应性聚合物或化合物功能化碳纳米材料,不仅可以提高其溶解性,还可以赋予其环境刺激响应功能。本文主要综述了近年来利用温度、pH、光以及CO2响应聚合物或小分子化合物对碳纳米管和石墨烯进行共价键、非共价键修饰并赋予其环境刺激响应特性的方法、功能和相关应用,展望了修饰得到的纳米碳杂化材料的应用前景及下一步发展方向。     

Near Infrared Organic Semiconducting Materials for Bulk Heterojunction and Dye‐Sensitized Solar Cells

Dye sensitized solar cells (DSSCs) and bulk heterojunction (BHJ) solar cells have been the subject of intensive academic interest over the past two decades, and significant commercial effort has been directed towards this area with the vison of developing the next generation of low cost solar cells. Materials development has played a vital role in the dramatic improvement of both DSSC and BHJ solar cell performance in the recent years. Organic conjugated polymers and small molecules that absorb solar light in the visible and near infrared (NIR) regions represent a class of emering materials and show a great potential for the use of different optoelectronic devices such as DSSCs and BHJ solar cells. This account describes the emering class of near infrared (NIR) organic polymers and small molecules having donor and acceptors units, and explores their potential applications in the DSSCs and BHJ solar cells.     

Recent strategies to enhance the performance of polymer monoliths for analytical separations

This review summarizes recent developments made in the incorporation of functional materials into organic polymer monoliths, together with new monolithic forms and formats, which enhance their application as supports and stationary phase materials for sample preparation and chromatographic separations. While polymer monoliths are well‐known supports for the separation of large molecules, recent developments have been made to improve their features for the separation of small molecules. The selectivity and performance of organic polymer monoliths has been improved by the incorporation of different materials, such as metal‐organic frameworks, covalent organic frameworks, or other types of nanostructured materials (carbon nanohorns, nanodiamonds, polyoxometalates, layered double hydroxides, or attapulgite). The surface area of polymer monoliths has been significantly increased by polymer hypercrosslinking, resulting in increased efficiency when applied to the separation of small molecules. In addition, recent exploration of less conventional supports for casting polymer monoliths, including photonic fibres and 3D printed materials, has opened new avenues for the applications of polymer monoliths in the field of separation science. Recent developments made in these topics are covered, focusing on the strategies followed by the authors to prepare the polymer monoliths and the effect of these modifications on the developed analytical applications.     

Organic Materials as Electrodes in Potassium-Ion Batteries

The integrated advantages of organic electrode materials and potassium metal make the organic potassium-ion batteries (OPIBs) promising secondary batteries. This review summarizes the latest research progress on OPIBs according to the different types of electrode materials (namely, organic small molecules compounds, polymers, and frameworks (metal–organic frameworks (MOFs), covalent organic frameworks (COFs)). Additionally, the research prospects and outlook for OPIBs are also provided.     

共价有机骨架材料设计及其在分离领域的应用

共价有机骨架(COFs)材料是由有机小分子单体通过共价键连接形成的结晶多孔聚合物。与传统的线性聚合物不同的是,COFs可以在二维和三维空间上对其骨架结构进行控制,从而合成具有高度有序的刚性多孔结构,并且能够调节骨架的化学和物理性质。这种由COF形成的纳米级孔道和空间为分子存储、释放和分离提供了理想的环境。因此它在能量储存、分离、催化等领域有着广泛的应用前景。本文综述了近年来COFs材料的研究进展,主要包括材料的合成策略及其在分离领域的应用,并对COFs材料未来的发展方向进行了展望。     

Chemical sensors based on π-conjugated organic molecules and gold nanoparticles

Scientists have developed techniques for synthesizing and characterizing many new materials including conjugated small molecules, polymers and gold particles protected by conjugated organic chromophores for testing specific sensing properties in the past decade. Still, the design and synthesis or supermolecular systems fabrication of novel materials with controlled sensing properties is a significant and ongoing challenge within nanoscience and nanotechnology. Recently, our group has successfully constructed a series of chemosensors using small organic molecules, conjugated polymers and gold nanoparticles for real-time detection of specific analytes. The chemosensors show high selectivity and sensitivity in the detection of cations and biologic analytes and thus are potentially promising for applications in sensing assay system. In this review, recent sutdies on the design, synthesis and photo-physical properties of novel materials and construct of chemosensors are summarized with an emphasis on the development in our groups in recent years. Supported by the National Natural Science Foundation of China (Grant Nos. 20531060, 20721061 & 20873155), and the National Basic Research 973 Programme of China (Grant No. 2007CB936401)     

Opto-electronic polymers for advanced computer and communication technologies

This paper describes reviews about the characterization of optical and electronic (opto-electronic) organic materials including polymers, and their applications for advanced key devices used for computers and communications technologies. On the basis of the author's recent investigations, discussions are made on organic electroluminescent thin film materials for emissive display devices, polymer-dispersed liquid crystal materials for passive display devices, organic photo-conductive materials for electrophotographic printer devices, and highly electroconductive polymers for solid tantalum capacitors. Finally, technical issues and development prospects for the opto-electronic organic materials in the 21st century are suggested.     

Covalent Organic Frameworks and Cage Compounds: Design and Applications of Polymeric and Discrete Organic Scaffolds

Porous organic materials are an emerging class of functional nanostructures with unprecedented properties. Dynamic covalent assembly of small organic building blocks under thermodynamic control is utilized for the intriguingly simple formation of complex molecular architectures in one‐pot procedures. In this Review, we aim to analyze the basic design principles that govern the formation of either covalent organic frameworks as crystalline porous polymers or covalent organic cage compounds as shape‐persistent molecular objects. Common synthetic procedures and characterization techniques will be discussed as well as more advanced strategies such as postsynthetic modification or self‐sorting. When appropriate, comparisons are drawn between polymeric frameworks and discrete organic cages in terms of their underlying properties. Furthermore, we highlight the potential of these materials for applications ranging from gas storage to catalysis and organic electronics.     

New low bandgap molecules based on ethylene-separated benzothiadiazoles: synthesis and bandgap comparison

New ethylene-separated benzothiadiazoles were synthesized for the first time by using a facile procedure, and they showed lower bandgaps than the reported benzothiadiazole-containing compounds. This new benzothiadiazole-containing unit could be introduced into the backbone of the π-conjugated small molecules or polymers to develop new materials with a low bandgap that may have potential applications in optoelectronic fields.     

Molecular design of star-shaped benzotrithiophene materials for organic electronics

Progresses in the design and application of conjugated small molecules, oligomers and polymers have empowered rapid development of organic electronic technology as an alternative to conventional devices. Among the numerous organic electronic materials, benzotrithiophene (BTT)-based oligomers and polymers have recently come in the limelight demonstrating great potential in organic electronics as high performance photovoltaic devices, field-effect transistors, electrochromic materials, high-area capacitors and charge carrier discotic liquid crystals. In this digest, we propose an overview of the organic electronic materials based on BTT isomers, highlighting the structure-performance relationship. The results obtained so far clearly indicate that the BTT isomers are among the most promising building blocks for the development π-extended materials for optoelectronic applications in the near future.     

Recent progress of electronic materials based on 2,1,3-benzothiadiazole and its derivatives: synthesis and their application in organic light-emitting diodes

2,1,3-Benzothiadiazole(BT) and its derivatives are very important acceptor units used in the development of photoluminescent compounds and are applicable for the molecular construction of organic light-emitting diodes, organic solar cells and organic field-effect transistors. Due to their strong electron-withdrawing ability, construction of molecules with the unit core of BT and its derivatives can usually improve the electronic properties of the resulting organic materials. In this contribution, we review the synthesis of various polymers, small molecules and metal complexes with BT and its derivatives and their applications in organic light-emitting diodes. Furthermore, the molecular design rules based on these cores are discussed.     

Optimizing the self-assembly of conjugated polymers and small molecules through structurally programmed non-covalent control

Organic conjugated polymers and oligomers are key electronic materials for applications such as transistors, photovoltaics, and light emitting devices due to their potential for solution processability, mechanical flexibility, and precise structure-based tuning compared to inorganic materials. In dilute environments, the optoelectronic properties of conjugated polymers are largely governed by their constitutional structure and, to a lesser degree, their solution-state intramolecular configuration. In the solid state, intramolecular conformation and intermolecular electronic coupling impact these properties substantially, especially in relation to device performance. Therefore, an increasingly important area of research concerning conjugated materials is developing design strategies aimed at optimizing the solid-state packing for electronic applications. Programming solid-state packing arrangements through discrete non-covalent interactions is an emerging strategy within the context of conjugated polymers. This review focuses on the use of the two most prevalent discrete and directional interactions used to dictate the self-assembly of conjugated polymers and oligomers—hydrogen bonds and chalcogen bonds. We also discuss how these design motifs can imbue conjugated materials with appealing physical properties while simultaneously retaining or improving electronic capabilities.     

Biomaterials made of bile acids

The use of natural compounds in the preparation of new materials can improve the biocompatibility of the materials and avoid any potential toxicity of the degradation products when used for biomedical applications. Bile acids are amphiphilic molecules biosynthesized in the liver. They are used to prepare various polymers and oligomers. These polymers made of bile acids are promising materials in both biomedical and pharmaceutical fields.     

基于胆酸的功能性分子的研究进展

胆酸是存在于人和动物体内的天然分子,由胆固醇在肝脏中合成．其结构上具有亲水的一面和憎水的一面,以其作为结构单元可以合成各种各样的功能性分子．这些分子因其独特的物理化学特性,被广泛应用到化学、生物医学等领域．本文回顾了近几年来国内外研究人员以胆酸为结构单元合成的高分子和低聚物及这些分子在生物医用材料方面的应用．     

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

A modular synthetic approach to degradable metathesis polymers is presented using acetal‐containing enyne monomers. The monomers are prepared in a short and divergent synthetic sequence that features two points of modification to tune polymerization behavior and introduce molecular cargo. Steric and stereochemical elements are critical in the monomer design in order to provide rapid and living polymerizations capable of generating block polymers. The developed polyacetal materials readily undergo pH‐dependent degradation in aqueous mixtures, and the rate of hydrolysis can be tuned through post‐polymerization modification with triazolinedione click chemistry. This presents a new scaffold for responsive metathesis polymers that may find use in applications that requires controllable breakdown and release of small molecules.     

Imprinted polymers-tailor-made mimics of antibodies and receptors

The technique of molecular imprinting allows the formation of specific recognition sites in synthetic polymers through the use of templates or imprint molecules. These recognition sites mimic the binding sites of antibodies and other biological receptor molecules. Molecularly imprinted polymers can therefore be used in applications relying on specific molecular binding events. The stability, ease of preparation and low cost of these materials make them particularly attractive. This review focuses on recent developments and advances in the field of molecularly imprinted materials, with special emphasis on applications in immunoassays and sensors recently developed by our group and by others.