Nanoporous materials: a good opportunity for nanosciences

This paper emphasizes the wide possibilities open to organometallic chemistry by the bottom-up approach for nanosciences. In this new field of research, organometallic chemistry and coordination chemistry are in position to play a very important role in the development of nanomaterials. At first, organometallic and coordination chemistries will be the mothers of plenty of nanotools, which are the elemental bricks of nanosciences. The nanomaterials are obtained from them either by inclusion in a matrix (Nanocomposites) or by grafting methods (grafted nanomaterials). However, the most exciting field of investigation are the nanostructured hybrid materials which permit to open new fields of investigation such as self-organization of organic moieties or the coordination chemistry in the solid. Some examples are given. Moreover, the organometallic chemistry performed on both the framework and the pores of the nanoporous solids obtained by sol-gel chemistry in the presence of structure directing agents is opening the way to smart materials. These materials will have the ability to couple interactively two different properties.     

New Synthetic Routes towards Soluble and Dissymmetric Triphenodioxazine Dyes Designed for Dye‐Sensitized Solar Cells

New π‐conjugated structures are constantly the subject of research in dyes and pigments industry and electronic organic field. In this context, the triphenodioxazine (TPDO) core has often been used as efficient photostable pigments and once integrated in air stable n‐type organic field‐effect transistor (OFET). However, little attention has been paid to the TPDO core as soluble materials for optoelectronic devices, possibly due to the harsh synthetic conditions and the insolubility of many compounds. To benefit from the photostability of TPDO in dye‐sensitized solar cells (DSCs), an original synthetic pathway has been established to provide soluble and dissymmetric molecules applied to a suitable design for the sensitizers of DSC. The study has been pursued by the theoretical modeling of opto‐electronic properties, the optical and electronic characterizations of dyes and elaboration of efficient devices. The discovery of new synthetic pathways opens the way to innovative designs of TPDO for materials used in organic electronics.     

Diketopyrrolopyrrole-based functional supramolecular polymers: next-generation materials for optoelectronic applications

The very concept of dye and pigment chemistry that was long known to the industrial world underwent a radical revision after the discovery and commercialization of dyes such as mauveine, indigo, and so on. Apart from their conventional role as coloring agents, organic dyes, and pigments have been identified as indispensable sources for high-end technological applications including optical and electronic devices. Simultaneous with the advancement in the supramolecular chemistry of π-conjugated systems and the divergent evolution of organic semiconductor materials, several dyes, and pigments have emerged as potential candidates for contemporary optoelectronic devices. Of all the major pigments, diketopyrrolopyrrole (DPP) better known as the ‘Ferrari Pigment’ and its derivatives have emerged as a major class of organic functional dyes that find varied applications in fields such as industrial pigments, organic solar cells, organic field–effect transistors, and in bioimaging. Since its discovery in 1974 by Farnum and Mehta, DPP-derived dyes gained rapid attention because of its attractive color, synthetic feasibility, ease of functionalization, and tunable optical and electronic properties. The advancement in supramolecular polymerization of DPP-based small molecules and oligomers with directed morphological and electronic features have led to the development of high performing optoelectronic devices. In this review, we highlight the recent developments in the optoelectronic applications of DPP derivatives specifically engineered to form supramolecular polymers.     

金属锗酸盐微纳米材料的研究进展

金属锗酸盐微纳米材料是一类非常重要的功能材料,展现出特殊的物理与化学性质,近年来已引起国内外学者浓厚的研究兴趣。迄今为止,人们已经利用多种合成方法制备了不同尺寸和形貌的锗酸盐微纳米材料。本文综述了目前这些材料制备方面的研究现状,简单比较了各种方法的优缺点;介绍了金属锗酸盐微纳米材料在光催化、重金属离子吸附、电化学传感、锂离子电池负极材料和光学器件等领域的应用,并展望了可能的发展趋势。     

分子识别指导下的有机分子设计、合成和组装——世纪交替时代的有机化学

在21世纪即将来临之际,有机化学将面临生命科学、环境科学和材料科学越来越多的挑战。本文回顾了在分子识别指导下的有机分子的设计、合成和组装这个新领域的诞生和发展,认为这个领域将成为新世纪有机化学发展的一个重要方向。它的发展和应用不仅使得有机化学可能较好地面对新挑战,同时能推动有机合成化学自身的发展。     

The supramolecular chemistry of organic-inorganic hybrid materials

The combination of nanomaterials as solid supports and supramolecular concepts has led to the development of hybrid materials with improved functionalities. These "hetero-supramolecular" ideas provide a means of bridging the gap between molecular chemistry, materials sciences, and nanotechnology. In recent years, relevant examples have been reported on functional aspects, such as enhanced recognition and sensing by using molecules on preorganized surfaces, the reversible building of nanometer-sized networks and 3D architectures, as well as biomimetic and gated chemistry in hybrid nanomaterials for the development of advanced functional protocols in three-dimensional frameworks. This approach allows the fine-tuning of the properties of nanomaterials and offers new perspectives for the application of supramolecular concepts.     

Tetrathiafulvalene: A Paradigmatic Electron Donor Molecule

Abstract

Tetrathiafulvalene (TTF) and its derivatives are exceptional building blocks in many areas of organic, supramolecular, and materials chemistry. Since the discovery ca. 30 years ago of the first “organic metal” tetrathiafulvalene-tetracyano-p-quinodimethane (TTF-TCNQ), a huge number of TTF derivatives have been synthetized.

Although initial efforts were directed to enhance the electron-donating ability of TTF analogues to improve the conductivities of salts and charge-transfer (CT) complexes derived from them, the developments in synthetic TTF chemistry have made it possible to incorporate TTF into more sophisticated structures such as materials exhibiting intramolecular charge-transfer and nonlinear optical properties, sensors, molecular shuttles and devices.

Compounds in which TTF and electron-accepting molecules, especially C ₆₀ , are covalently tethered exhibit outstanding photophysical properties leading, upon photoexcitation, to charge-separated (CS) states showing remarkable lifetimes. In these systems, the gain of aromaticity upon oxidation of the TTF moiety has been used as a new concept for improving the stability of the charge-separated state, and, therefore, are of interest for the preparation of artificial photosynthetic systems as well as photovoltaic devices.     

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.     

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。     

碳点的制备及荧光量子产率的测定 ——一个仪器分析综合实验

As a new type of nano-materials, carbon dots have unique optical properties and excellent chemical properties, such as easy preparation, low cost, high chemical stability and good biocompatibility. Three kinds of carbon dots were prepared by microwave, hydrothermal and pyrolysis methods, and characterized by infrared spectroscopy. The ultraviolet-visible absorption spectra and fluorescence spectra of the three carbon dots were measured and compared with those of small organic fluorescent molecules. The fluorescence quantum yield of three carbon dots was measured using quinine sulfate as standards. This experiment not only enables students to learn the preparation methods and the unique luminescent properties of carbon nanomaterials, but also enables students to have a deeper understanding of the structures, principles and applications of three kinds of molecular spectroscopy instruments based on the measurement of quantum yield. This experiment can be used as a comprehensive 10-hour instrumental analysis experiment for junior students majoring in chemistry, applied chemistry and material chemistry.     

BN-embedded aromatics for optoelectronic applications

The knowledge of azaborine chemistry is growing as an important branch in organic semiconductor materials. Specifically, BN-embedded aromatic compounds have attracted great attention due to their fascinating properties resulted from the replacement of CC unit with isoelectronic BN unit in aromatics. Though great insights have been provided into the synthetic chemistry and photophysical properties of BN-embedded aromatics, their applications in optoelectronic areas are still at a young stage. This short review summarizes the recent progress of BN-embedded aromatics with optoelectronic applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, stimuli-responsive luminescent devices, and chemical sensors.     

Nanomaterials for rechargeable lithium batteries

Energy storage is more important today than at any time in human history. Future generations of rechargeable lithium batteries are required to power portable electronic devices (cellphones, laptop computers etc.), store electricity from renewable sources, and as a vital component in new hybrid electric vehicles. To achieve the increase in energy and power density essential to meet the future challenges of energy storage, new materials chemistry, and especially new nanomaterials chemistry, is essential. We must find ways of synthesizing new nanomaterials with new properties or combinations of properties, for use as electrodes and electrolytes in lithium batteries. Herein we review some of the recent scientific advances in nanomaterials, and especially in nanostructured materials, for rechargeable lithium-ion batteries.     

Controlled self-assembly of alkylated-π compounds for soft materials — Towards optical and optoelectronic applications

Organic and polymeric molecules based on π-conjugated units represent an important class of components for optical and optoelectronic functionalized soft materials. Inspired by the innovative molecular design made by synthetic chemists, new functions and applications of π-conjugated molecules are continuously emerging. However, a challenge that remains is to soften these molecules. Alkylation is a commonly employed synthetic strategy to achieve functionalization in order to improve processability, i.e., solubility in volatile solvents, for better utilization in the rapidly-developing field of organic electronics. In addition it is recognized as a powerful strategy to tune the interaction among the π-conjugated moieties. In a different interpretation of alkylation, alkylated-π compounds can be viewed as a class of hydrophobic amphiphiles, since the rigid π-conjugated moiety and flexible alkyl chains are intrinsically immiscible. Recent studies have shown that such compounds can form a variety of self-organized solid and thermotropic liquid crystalline structures as well as nonassembled liquid forms depending upon the position, number and kinds of attached alkyl chains. Here, we present a brief overview of recent developments of alkylated-π chemistry, with an emphasis on the relationships between molecular design, self-assembly behavior and applications in optical and optoelectronic devices. We hope this review can serve as a guide and reference for people working in different research areas, including self-assembly and colloid sciences, synthetic and materials chemistry was well as organic electronics.     

Dispersions, novel nanomaterial sensors and nanoconjugates based on carbon nanotubes

Nanomaterials are structures with dimensions characteristically much below 100 nm. The unique physical properties (e.g., conductivity, reactivity) have placed these nanomaterials in the forefront of emerging technologies. Significant enhancement of optical, mechanical, electrical, structural, and magnetic properties are commonly found through the use of novel nanomaterials. One of the most exciting classes of nanomaterials is represented by the carbon nanotubes. Carbon nanotubes, including single-wall carbon nanotubes, multi-wall carbon nanotubes, and concentric tubes have been shown to possess superior electronic, thermal, and mechanical properties to be attractive for a wide range of potential applications They sometimes bunch to form “ropes” and show great potential for use as highly sensitive electronic (bio)sensors due to the very small diameter, directly comparable to the size of single analyte molecules and that every single carbon atom is in direct contact with the environment, allowing optimal interaction with nearby molecules. Composite materials based on integration of carbon nanotubes and some other materials to possess properties of the individual components with a synergistic effect have gained growing interest. Materials for such purposes include conducting polymers, redox mediators and metal nanoparticles. These tubes provide the necessary building blocks for electronic circuits and afford new opportunities for chip miniaturization, which can dramatically improve the scaling prospects for the semiconductor technologies and the fabrication of devices, including field-effect transistors and sensors. Carbon nanotubes are one of the ideal materials for the preparation of nanoelectronic devices and nanosensors due to the unique electrical properties, outstanding electrocatalytic properties, high chemical stability and larger specific surface area of nanotubes. Carbon nanotubes are attractive material for supercapacitors due to their unique one-dimensional mesoporous structure, high specific surface area, low resistivity and good chemical stability. Nanoscaled composite materials based on carbon nanotubes have been broadly used due to their high chemical inertness, non-swelling effect, high purity and rigidity. The integration of carbon nanotubes with organics, biomaterials and metal nanoparticles has led to the development of new hybrid materials and sensors. Hybrid nanoscale materials are well established in various processes such as organic and inorganic compounds, nucleic acid detachment, protein separation, and immobilization of enzymes. Those nanostructures can be used as the building blocks for electronics and nanodevices because uniform organic and metal coatings with the small and monodisperse domain sizes are crucial to optimize nanoparticle conductivity and to detect changes in conductivity and absorption induced by analyte adsorption on these surfaces. The highly ordered assembly of zero-dimensional and one-dimensional nanoparticles is not only necessary for making functional devices, but also presents an opportunity to develop novel collective properties.     

Functionalization of mesostructured inorganic–organic and porous inorganic materials

The capability to functionalize the interior channels and/or high internal surface areas of mesostructured inorganic–organic or porous inorganic solids with specific organic or inorganic moieties has dramatically expanded the potential applications for these versatile materials in catalysis, separations, optical and opto-electronic devices, drug delivery, sensors, and energy conversion. Key to the widespread application of these materials are the various synthetic schemes that have been developed to provide control over the types of species incorporated and, more importantly, their distributions within the mesostructured hosts. Furthermore, multiple active species can often be independently incorporated and collectively optimized to yield multifunctional properties that widen application prospects. Several recent developments and examples in this rapidly growing field of materials chemistry and engineering are highlighted and discussed.     

Recent applications of carbon-based nanomaterials in analytical chemistry: critical review

The objective of this review is to provide a broad overview of the advantages and limitations of carbon-based nanomaterials with respect to analytical chemistry. Aiming to illustrate the impact of nanomaterials on the development of novel analytical applications, developments reported in the 2005-2010 period have been included and divided into sample preparation, separation, and detection. Within each section, fullerenes, carbon nanotubes, graphene, and composite materials will be addressed specifically. Although only briefly discussed, included is a section highlighting nanomaterials with interesting catalytic properties that can be used in the design of future devices for analytical chemistry.     

Carbohydrate-derived porous carbon materials: An ideal platform for green organic synthesis

Porous carbon materials have attracted much attention in the field of organic synthesis in recent years,due to their tunable properties, excellent catalytic activity and stability. Biomass-based carbohydrates emerge as an ideal precursor for the generation of these materials owing to their renewability, low cost,non-toxicity and high content of functional groups. Thus, carbon materials prepared from carbohydrates is of considerable importance for the sustainable development of organic chemistry....     

Synthesis and modification of silicon nanosheets and other silicon nanomaterials

Silicon nanomaterials and nanostructures exhibit different properties from those of bulk silicon materials based on quantum confinement effects. They are expected to lead to the development of new applications of silicon, in addition to wide use in semiconductor devices. Aside from industrial interest, intriguing issues of academic interest still remain with respect to the origins of their characteristic properties. Zero- and one-dimensional crystalline silicon nanomaterials have been synthesized, to date, by using many methods and there has been rapid progress in size control and modification procedures. However, there have been only a few examples of silicon nanomaterials with atomic-order thickness akin to carbon nanomaterials, such as two-dimensional silicon nanosheets. Moreover, mass production of silicon nanomaterials with relatively low cost is not easily achievable, due to the typically severe conditions required for fabrication, such as high temperature and ultralow pressure. Recently, we have developed a soft synthetic method for silicon nanosheets with chemical surface modification in a solution process. This review provides methods for the synthesis and modification of silicon nanosheets and other silicon nanomaterials with examples of their potential applications.     

Synthesis and properties of colloidal heteronanocrystals

Colloidal heteronanocrystals (HNCs) can be regarded as solution-grown inorganic-organic hybrid nanomaterials, since they consist of inorganic nanoparticles that are coated with a layer of organic ligand molecules. The hybrid nature of these nanostructures provides great flexibility in engineering their physical and chemical properties. The inorganic particles are heterostructured, i.e. they comprise two (or more) different materials joined together, what gives them remarkable and unique properties that can be controlled by the composition, size and shape of each component of the HNC. The interaction between the inorganic component and the organic ligand molecules allows the size and shape of the HNCs to be controlled and gives rise to novel properties. Moreover, the organic surfactant layer opens up the possibility of surface chemistry manipulation, making it possible to tailor a number of properties. These features have turned colloidal HNCs into promising materials for a number of applications, spurring a growing interest on the investigation of their preparation and properties. This critical review provides an overview of recent developments in this rapidly expanding field, with emphasis on semiconductor HNCs (e.g., quantum dots and quantum rods). In addition to defining the state of the art and highlighting the key issues in the field, this review addresses the fundamental physical and chemical principles needed to understand the properties and preparation of colloidal HNCs (283 references).     

离子液体固定化材料在固相萃取中的应用研究进展

离子液体是由阴、阳离子组成的低温熔融盐,几乎没有蒸汽压,具有稳定性好、溶解能力强、结构可设计、导电性好等优良性能。离子液体作为一种广受关注的新型“绿色溶剂”,具有代替传统有机溶剂的潜力,其制备方法和应用范围研究日趋完善和多样,已广泛应用于催化化学、光电化学、材料化学和分析化学等领域。离子液体通过功能化导向设计后,可以将羟基、氨基、羧基、氰基等活性基团键合在离子液体结构上,促使其更加易于与目标分子通过生成π-π键、氢键、离子键和范德华力等而产生相互作用,更加易于发生固定化反应。将离子液体负载到固体载体材料进行固定化后,新型材料既可以减少离子液体的流失,同时保留了离子液体和固体载体的独特性能,具有富集效率高、吸附容量高、稳定性好、识别位点多、萃取选择性强、离子液体利用率高等特点,近年来,在有机小分子固相萃取分离研究中应用广泛。该文从离子液体与硅胶、分子筛、分子印迹聚合物、氧化石墨烯、磁性材料等固体载体的固定化研究情况入手,综述了离子液体固定化材料在固相萃取分离中的应用情况,涉及的目标分离物质包括生物碱类、黄酮类、多酚类等天然活性成分,以及常见药物分子、有机农药等有机小分子化合物,系统地介绍了离子液体与多种载体固定化的性质、应用和分离机制。离子液体的引入,增加了复合材料的活性位点分布和吸附容量,离子液体固定化材料的吸附效率与离子液体种类、吸附材料用量、样品溶液浓度、吸附温度、pH值、洗脱溶剂类型、用量及流速等因素有关。该文探讨了离子液体结构相对单一、相关基础理论研究相对薄弱、复杂基质萃取程度不理想等问题,并提出相应的解决思路,以期为离子液体固定化材料在复杂基质中目标分子分离分析方面的应用提供借鉴和参考。