Progress of Indeno-type Organic Diradicaloids

Organic diradicaloids have unusual open-shell nature and properties and are promising materials for organic electronics, spintronics, energy storage and nonlinear optics. In this review, we focus on indeno-type organic diradicaloids and summarize their molecular design and synthesis, as well as topological structures, open-shell characters and diradical properties. The molecular systems are classified into indenofluorenes and diindenoacenes, indeno-based molecules with one-dimensional, two-dimensional and unique topological structures, and heterocyclic indeno-based molecules. By constructing these various topological π-skeletons with tunable conjugation modes and variation of atomic composition, their key open-shell parameters, such as diradical characters and singlet-triplet energy gaps, along with the optical, electronic and magnetic properties, as well as stabilities are efficiently modulated. More attention may be paid to accurate computational analysis, rational design and synthesis, and novel functions of indeno-type diradicaloids, which will promote the development of radical chemistry and materials.     

二氧化钛多孔材料及其性能研究进展

二氧化钛(TiO₂)多孔材料由于具有优异的物理化学性质,在催化、能源、传感等领域展现了重要的研究价值和应用潜力。 TiO₂的多孔结构特别在一些涉及异相反应的应用(如异相催化、气敏等)中具有重要的优势,如丰富的传质通道和表面活性位点、可调变的孔尺寸等。 目前,多孔TiO₂功能材料的开发和优化研究正在不断推进其工业化应用的进程。 本文围绕多孔TiO₂的几个优势应用领域(光催化、光生电子存储和气敏)的研究进展,从结构和缺陷设计出发介绍和讨论性能调控策略。 本文还特别介绍了本课题组通过光诱导合成法开发的一系列多孔TiO₂基功能材料,并对相关性能研究领域的关键问题进行了分析和展望。     

无机分子纳米材料的研究进展

无机分子纳米材料是至少在一个维度上为纳米尺寸的分子及以其为单元组成的材料。由于其特殊的结构和性质，这种材料可以作为未来纳米分子电子器件、小分子吸附及储存材料。本文将从合成、结构、性质、应用等方面, 结合最新进展对这一充满活力并有着应用前景的领域作一简要概述。     

Optical waveguides at micro/nanoscale based on functional small organic molecules

Optical waveguides synthesized at the micro/nanoscale have drawn great interest for their potential applications in high speed miniaturized photonic integrations. In this Perspective article, we mainly focus on the related works on active optical waveguides based on functional small organic molecules in micro/nano regime. We begin with a general overview of recent progress in sub-wavelength optical waveguides, including the development of waveguide materials of inorganic semiconductors, polymers, and small organic molecules. Then brief highlights are put on the recently reported organic optical waveguides with various unique optical properties induced by the ordered molecular aggregations in the micro/nano-sized solid-state structures, such as polarized emission, lasing, aggregation-induced enhanced emission, etc. This article concludes with a summary and our personal view about the direction of future development in organic opto-functional waveguides as photonic devices.     

有序介孔材料在生物医药领域中的应用

本文简述了有序介孔材料的特性,详细介绍了其在生物医药领域中的应用研究,如用于酶的固定化、生物传感器、药物的包埋和控释、生物活性材料、生物分子的吸附和分离等,阐述了不同类型的有序介孔材料在这些应用中的性能以及为适用于该领域应用进行的材料开发和结构修饰,最后对材料的改进和应用前景进行了展望。     

Synthesis of Metallic Nanoparticles Using Closed‐Shell Structures as Templates

The synthesis and study of metallic nanoparticles are of continued and significant interest, with applications in materials science, catalysis, and medicine. The properties of metallic nanoparticles depend strongly on their particle size, shape, and interparticle distances. It is therefore desirable for the synthesis of metallic nanoparticles to be controlled for specific shapes and sizes. The rapid development in this research area has attracted intense interest from researchers with diverse expertise, and numerous methods towards the synthesis of monodisperse nanoparticles have been reported. In this Focus Review, we provide an overview of recent progress in the development of the template synthesis of metallic nanoparticles using closed‐shell structures, including biological molecules/assemblies and cage molecules.     

Strictly Biphasic Soft and Hard Janus Structures: Synthesis,Properties, and Applications

Janus structures, named after the ancient two‐faced Roman god Janus, comprise two hemistructures (e.g. hemispheres) with different compositions and functionalities. Much research has been carried out over the past few years on Janus structures because of the intriguing properties and promising potential applications of these unusually shaped materials. This Review discusses recent progress made in the synthesis, properties, and applications of strictly biphasic Janus structures possessing symmetrical structures but made of disparate materials. Depending on the chemical compositions, such biphasic structures can be categorized into soft, hard, and hybrid soft/hard Janus structures of different architectures, including spheres, rodlike, disclike, or any other shape. The main synthetic routes to soft, hard, and hybrid soft/hard Janus structures are summarized and their unique properties and applications are introduced. The perspectives for future research and development are also described.     

Hydrophilic Conjugated Materials for Photocatalytic Hydrogen Evolution

Photocatalytic hydrogen evolution is viewed as a promising green strategy to utilize the inexhaustible solar energy and provide clean hydrogen fuels with zero‐emission characteristic. The nature of semiconductor‐based photocatalysts is the key point to achieve efficient photocatalytic hydrogen evolution. Conjugated materials have been recently emerging as a novel class of photocatalysts for hydrogen evolution and photocatalytic reactions due to their electronic properties can be well controlled via tailor‐made chemical structures. Hydrophilic conjugated materials, a subgroup of conjugated materials, possess multiple advantages for photocatalytic applications, thus spurring remarkable progress on both material realm and photocatalytic applications. This minireview aims to provide a brief review of the recent developments of hydrophilic conjugated polymers/small molecules for photocatalytic applications, and special concern on the rational molecular design and their impact on photocatalytic performance will be reviewed. Perspectives on the hydrophilic conjugated materials and challenges to their applications in the photocatalytic field are also presented.     

A molecular bowl sumanene

Nonplanar polyaromatic carbon molecules including fullerenes and carbon nanotubes have been attracting great interest due to their potential as materials, catalysts, etc. In this context, bowl-shaped polyaromatic hydrocarbons (π bowls) are considered to be key materials in the science of nonplanar π-conjugated carbon systems. Among π bowls, we focused on a molecular bowl "sumanene (C(21)H(12))" featuring a C(3v) symmetric structural motif present in fullerenes or carbon nanotube molecules. In this article, we present the research on sumanenes to date, including their synthesis, structural characterization, derivatization, complexation, and their potential uses as electrical materials. The characteristic structural feature of a sumanene depends on three sp(3) hybridized carbon atoms at the benzylic positions. Facile functionalization via selective formation of benzylic anions gives stereoselective substituted compounds, the π-extended derivatives, and the deeper π bowls. Furthermore, the dynamically flexible aspect based on bowl-to-bowl inversion is also described. The crystal with a columnar bowl-in-bowl stacking exhibits a high electron transport ability with anisotropy. Complexation with a cyclopentadienyl iron cation results in the first selective formation of the concave-bound complex as a π-bowl complex.     

Understanding and Designing Thermally Activated Delayed Fluorescence Emitters: Beyond the Energy Gap Approximation

In this article recent progress in the development of molecules exhibiting Thermally Activated Delayed Fluorescence (TADF) is discussed with a particular focus upon their application as emitters in highly efficient organic light emitting diodes (OLEDs). The key aspects controlling the desirable functional properties, e. g. fast intersystem crossing, high radiative rate and unity quantum yield, are introduced with a particular focus upon the competition between the key requirements needed to achieve high performance OLEDs. The design rules required for organic and metal organic materials are discussed, and the correlation between them outlined. Recent progress towards understanding the influence of the interaction between a molecule and its environment are explained as is the role of the mechanism for excited state formation in OLEDs. Finally, all of these aspects are combined to discuss the ability to implement high level design rules for achieving higher quality materials for commercial applications. This article highlights the significant progress that has been made in recent years, but also outlines the significant challenges which persist to achieve a full understanding of the TADF mechanism and improve the stability and performance of these materials.     

A Review on Graphene Oxide Two-dimensional Macromolecules: from Single Molecules to Macro-assembly

Graphene oxide(GO), which consists of two-dimensional(2 D) sp² carbon hexagonal networks and oxygen-contained functional groups, has laid the foundation of mass production and applications of graphene materials. Made by chemical oxidation of graphite, GO is highly dispersible or even solubilized in water and polar organic solvents, which resolves the hard problem of graphene processing and opens a door to wet-processing of graphene. Despite its defects, GO is easy to functionalize, dope, punch holes, cut into pieces, conduct chemical reduction, form lyotropic liquid crystal, and assemble into macroscopic materials with tunable structures and properties as a living building block. GO sheet has been viewed as a single molecule, a particle, as well as a soft polymer material. An overview on GO as a 2 D macromolecule is essential for studying its intrinsic properties and guiding the development of relevant subjects. This review mainly focuses on recent advances of GO sheets, from single macromolecular behavior to macro-assembled graphene material properties. The first part of this review offers a brief introduction to the synthesis of GO molecules. Then the chemical structure and physical properties of GO are presented, as well as its polarity in solvent and rheology behavior. Several key parameters governing the ultimate stability of GO colloidal behavior, including size, p H and the presence of cation in aqueous dispersions, are highlighted. Furthermore, the discovery of GO liquid crystal and functionalization of GO molecules have built solid new foundations of preparing highly ordered, architecture-tunable, macro-assembled graphene materials, including 1 D graphene fibers, 2 D graphene films, and 3 D graphene architectures. The GO-based composites are also viewed and the interactions between these target materials and GO are carefully discussed. Finally, an outlook is provided in this field, where GO is regarded as macromolecules, pointing out the challenges and opportunities that exist in the field. We hope that this review will be beneficial to the understanding of GO in terms of chemical structure,molecular properties, macro-assembly and potential applications, and encourage further development to extend its investigations from basic research to practical applications.     

Multifunctional Organic Emitters for High‐Performance and Low‐Cost Organic Light‐Emitting Didoes

Organic light‐emitting diodes (OLEDs) have great potential applications in display and solid‐state lighting. Stability, cost and high operational efficiency are key issues governing the future commercial application of OLEDs. In this context, searching for multifunctional emitting materials with acceptable light‐emitting and charge‐transporting characteristics has gained increasing attention. For achieving high‐performance and low‐cost OLEDs, the suitable molecular design featured with different electronic and optical nature should be incorporated by combining the advantages of both functional units into the same molecules. This review highlights recent and current advances in developing bifunctional or multifunctional molecules, with the focus on structures, properties, and applications in OLEDs and organic laser.     

Recent progress of sugar amino acids: Synthetic strategies and applications as glycomimetics and peptidomimetics

In order to meet the increasing demands for the development of large varieties of new molecules for discovering new drugs and materials, organic chemists are developing many novel multifunctional building blocks, which are assembled rationally to create ‘nature-like' and yet unnatural organic molecules with well-defined structures and useful properties. Sugar amino acids(SAAs), the carbohydrate derivatives bearing both amino and carboxylic acid functional groups, are important ones of these multifunctional building blocks, which can be used to create novel materials with potential applications as glycomimetics and peptidomimetics. This review will focus on recent synthetic strategies of SAAs and their applications in creating large number of structurally diverse glycomimetics and peptidomimetics.     

基于磷光材料的电致发光二极管研究进展

电致发光二极管(LEDs)具有能耗低、寿命长、绿色环保等优点,在固态照明、全色显示等领域具有广阔的应用前景。 与传统的荧光电致LEDs相比,磷光电致LEDs能够同时利用单重态和三重态激子,理论上可以使器件的内量子效率达到100%,突破5%的外量子效率极限。 因此,发展高效的磷光材料以及实现其在电致LEDs中的应用是非常有意义的。 本文综述了目前主要的磷光材料,包括有机金属配合物、纯有机分子、聚合物、金属有机框架材料和碳量子点等,并总结了稀有金属配合物和纯有机分子在电致磷光 LEDs中的研究进展,同时对电致磷光LEDs的发展前景进行展望。     

Biomimetic and bioinspired silica: recent developments and applications

In a previous review of biological and bioinspired silica formation (S. V. Patwardhan et al., Chem. Commun., 2005, 1113 [ref. 1]), we have identified and discussed the roles that organic molecules (additives) play in silica formation in vitro. Tremendous progress has been made in this field since and this review attempts to capture, with selected examples from the literature, the key advances in synthesising and controlling properties of silica-based materials using bioinspired approaches, i.e. conditions of near-neutral pH, all aqueous environments and room temperature. One important reason to investigate biosilicifying systems is to be able to develop novel materials and/or technologies suitable for a wide range of applications. Therefore, this review will also focus on applications arising from research on biological and bioinspired silica. A range of applications such as in the areas of sensors, coatings, hybrid materials, catalysis and biocatalysis and drug delivery have started appearing. Furthermore, scale-up of this technology suitable for large-scale manufacturing has proven the potential of biologically inspired synthesis.     

Fluorescent assemblies: Synergistic of amphiphilic molecules and fluorescent elements

In recent years, fluorescent assemblies based amphiphilic molecules have gained attention as unique and powerful materials for multiple applications that cover sensors, optoelectronics and bioimaging because of amphiphilic molecules self-assembly with outstanding flexibility and diversity spanning assembly structure from micelles, vesicles and nano-assemblies to gels. Weak and noncovalent interactions are important driving force for assemblies. The combination of the structural characteristics of self-assembly and the fluorescent properties of the fluorescent building element render the fluorescent material versatility and their easy-to-tune properties. Amphiphilic molecules can be used as building elements to co-assemble with dye molecules, aggregation-induced emission (AIE) gens, fluorescent nanoparticles and new amphiphilic molecules containing fluorescent groups can also be designed and prepared with self-assembly capability. Concomitantly, the improvement of fluorescence performance including fluorescence intensity, quantum yield, stability and controllability during assembly proved outstanding properties of fluorescence assemblies. These promising fluorescent assemblies are by far not exhaustive in construction method and mechanism explanation but foreshadow their more potential applications. Here, we will understand deeper the fluorescent assemblies and inspire future developments and applications employing this emerging fluorescence soft materials.     

Recent advances of folded tetraphenylethene derivatives featuring through-space conjugation

Through-space conjugated molecules are interesting building blocks for the construction of functional materials that allow multi-dimensional transport of carrier and energy. However, the well explored through-space conjugated molecules are quite limited, which defers their structure-property correlation establishment and wide-scale application. In this review, we introduce a kind of newly-emerging folded tetraphenylethene derivatives featuring through-space conjugation. Their synthesis, crystal and electronic structures, and optical properties are described, and their representative applications as bipolar charge-transporting materials in organic light-emitting diodes and as single-molecule wires in molecular devices are presented, which are anticipated to provide guidance for the further expansion of through-space conjugated systems.     

Lanthanide‐Based Luminescent Materials for Waveguide and Lasing

Microlasers and waveguides have wide applications in the fields of photonics and optoelectronics. Lanthanide‐doped luminescent materials featuring large Stokes/anti‐Stokes shift, long excited‐state lifetime as well as sharp emission bandwidth are excellent optical components for photonic applications. In the past few years, great progress has been made in the design and fabrication of lanthanide‐based waveguides and lasers at the micrometer length scale. Waveguide structures and microcavities can be fabricated from lanthanide‐doped amorphous materials through top‐down process. Alternatively, lanthanide‐doped organic compounds featuring large absorption cross‐section can self‐assemble into low‐dimensional structures of well‐defined size and morphology. In recent years, lanthanide‐doped crystalline structures displaying highly tunable excitation and emission properties have emerged as promising waveguide and lasing materials, which substantially extends the range of lasing wavelength. In this minireview, we discuss recent advances in lanthanide‐based luminescent materials that are designed for waveguide and lasing applications. We also attempt to highlight challenging problems of these materials that obstacle further development of this field.     

Clusteroluminescence: A gauge of molecular interaction

Clusteroluminescence (CL) materials, as an emerging class of luminescent materials with unique photophysical properties, have received increasing attention owing to their great theoretical significance and potential for biological applications. Although much progress has been made in the design, synthesis and application of CL materials, there is still a big challenge in the emission mechanism. So far, through-space interaction has been proposed as the preliminary mechanism of the corresponding clusterization-triggered emission (CTE) effect, but a systematic theory is still needed. This review summarizes the current mechanistic understanding of CL materials including organic/inorganic small molecules, and polymers with/without isolated aromatic structures. In addition, some strategies to achieve high quantum yield, adjustable emission color, and persistent room temperature phosphorescence in CL materials are also summarized. At last, a perspective of the mechanism and application of CL materials are demonstrated, which inspire the researchers working on the development of new kinds of functional materials.     

Surface modification of natural cellulose substances:toward functional materials and applications

Combining various synthetic chemical processes and biological assemblies provides a promising strategy for the design and fabrication of functional materials with tailored structures and properties.The unique multilevel structures and morphologies of natural cellulose substances such as ordinary commercial laboratory filter paper make them ideal platforms for the self-assemblies of various functional guest molecules that are to be deposited on the surfaces of their fine structures,and the resulting composite matters show significant potentials for various applications.The surface sol-gel process was employed to deposit ultrathin metal-oxide(e.g.,titania and zirconia)gel films to coat the cellulose nanofibers in bulk filter papers;thereafter,monolayers of specific guest substrates were immobilized onto the surfaces of the metal-oxide gel films.Highly selective,sensitive,and reversible chemosensors based on the surface modification of filter paper were obtained toward the fluorescence and colorimetric detection of various analytes such as heavy-metal ions,inorganic anions,amino acids,and gases.Cellulosebased composite materials with superhydrophobic,antibacterial,or luminescent properties were fabricated by self-assembly approaches toward practical applications.