High-load, hybrid Si-ROMP reagents

The combination of norbornenyl-tagged (Nb-tagged) silica particles and functionalized Nb-tagged monomers for the generation of hybrid Si-ROMP reagents and scavengers is reported. Specifically Si-ROMP-derived bis-acid chloride, dichlorotriazine, and triphenylphosphine scavenger/reagents have been grafted from the surface of silica particles utilizing surface-initiated, ring-opening metathesis polymerization (ROMP). These hybrid polymeric materials combine the physical properties of current immobilized silica reagents and represent a key advancement in load by merging the inherent tunable properties of the ROMP-derived oligomers with silica supports for application in a parallel synthesis.     

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....     

Ultralong organic room-temperature phosphorescence of electron-donating and commercially available host and guest molecules through efficient F?rster resonance energy transfer

Ultralong organic room-temperature phosphorescence(RTP) materials have attracted tremendous attention recently due to their diverse applications. Several ultralong organic RTP materials mimicking the host-guest architecture of inorganic systems have been exploited successfully. However, complicated synthesis and high expenditure are still inevitable in these studies. Herein, we develop a series of novel host-guest organic phosphorescence systems, in which all luminophores are electron-rich, commercially available and halogen-atom-free. The maximum phosphorescence efficiency and the longest lifetime could reach 23.6% and 362 ms, respectively. Experimental results and theoretical calculation indicate that the host molecules not only play a vital role in providing a rigid environment to suppress non-radiative decay of the guest, but also show a synergistic effect to the guest through F?rster resonance energy transfer(FRET). The commercial availability, facile preparation and unique properties also make these new host-guest materials an excellent candidate for the anti-counterfeiting application. This work will inspire researchers to develop new RTP systems with different wavelengths from commercially available luminophores.     

Modern separation techniques for the efficient workup in organic synthesis

The shift of paradigm in combinatorial chemistry, from large compound libraries (of mixtures) on a small scale towards defined compound libraries where each compound is prepared in an individual well, has stimulated the search for alternative separation approaches. The key to a rapid and efficient synthesis is not only the parallel arrangement of reactions, but simple work-up procedures so as to circumvent time-consuming and laborious purification steps. During the initial development stages of combinatorial synthesis it was believed that rational synthesis of individual compounds could only be achieved by solid-phase strategies. However, there are a number of problems in solid-phase chemistry: most notably there is the need for a suitable linker unit, the limitation of the reaction conditions to certain solvents and reagents, and the heterogeneous reaction conditions. Further disadvantages are: the moderate loading capacities of the polymeric support and the limited stability of the solid support. In the last few years several new separation techniques have been developed. Depending on the chemical problem or the class of compounds to be prepared, one can choose from a whole array of different approaches. Most of these modern separation approaches rely on solution-phase chemistry, even though some of them use solid-phase resins as tools (for example, as scavengers). Several of these separation techniques are based on liquid-liquid phase separation, including ionic liquids, fluorous phases, and supercritical solvents. Besides being benign with respect to their environmental aspects, they also show a number of advantages with respect to the work-up procedures of organic reactions as well as simplicity in the isolation of products. Another set of separation strategies involves polymeric supports (for example, as scavengers or for cyclative cleavage), either as solid phases or as soluble polymeric supports. In contrast to solid-phase resins, soluble polymeric supports allow reactions to be performed under homogeneous conditions, which can be an important factor in catalysis. At the same time, a whole set of techniques has been developed for the separation of these soluble polymeric supports from small target molecules. Finally, miscellaneous separation techniques, such as phase-switchable tags for precipitation by chemical modification or magnetic beads, can accelerate the separation of compounds in a parallel format.     

Phenolic Building Blocks for the Assembly of Functional Materials

Phenolic materials have long been known for their use in inks, wood coatings, and leather tanning. However, there has recently been a renewed interest in engineering advanced materials from phenolic building blocks. The intrinsic properties of phenolic compounds, such as metal chelation, hydrogen bonding, pH responsiveness, redox potentials, radical scavenging, polymerization, and light absorbance, have made them a distinct class of structural motifs for the synthesis of functional materials. Materials prepared from phenolic compounds often retain many of these useful properties with synergistic effects in applications ranging from catalysis to biomedicine. This Review provides an overview of the diverse functional materials that can be prepared from natural and synthetic phenolic building blocks, as well as their applications.     

Organic nanocrystals grown in sol-gel matrices: new hybrid organic-inorganic materials for optics

We have developed a simple and generic preparation of stable organic nanocry stals grown in gel-glass matrices. The synthesis of these hybrid organic-inorganic materials is based on the confined nucleation and growth of organic phases in the pores of dense gels. For bulk nanocomposite samples, narrow size distributions of particles (10–20 nm in diameter) are obtained. We have extended this method to the preparation of organic nanocrystals embedded in sol-gel thin films prepared by spin-coating. For all these nanocomposite materials, we have significantly increased the dye stability and obtained promising optical properties: luminescence, non-linear optical properties or photochromism. Moreover, we have also demonstrated basic working principles of a new type of fluorescent nanosensor through the preparation of organic luminescent nanocrystals grown in silicate films.     

Organophosphorus π-conjugated materials: the rise of a new field

The synthesis and electronic properties of new linear organic π-conjugated systems incorporating phosphole rings are described. Well defined α,α′-(phosphole-thiophene) oligomers possess low HOMO-LUMO gaps and their optical and electrochemical properties can be tuned via chemical modifications of the P-atoms. The physical properties of these compounds make them valuable materials for OLED’s. The coordination ability of phosphole-based dipoles has been exploited for the synthesis of efficient multipolar NLO-phores. Lastly, phospholes have been used for the synthesis of assemblies exhibiting through-bond interaction between two π-systems via P-P σ-skeletons.     

Self-assembled gelators for organic electronics

Nature excels at engineering materials by using the principles of chemical synthesis and molecular self-assembly with the help of noncovalent forces. Learning from these phenomena, scientists have been able to create a variety of self-assembled artificial materials of different size, shapes, and properties for wide ranging applications. An area of great interest in this regard is solvent-assisted gel formation with functional organic molecules, thus leading to one-dimensional fibers. Such fibers have improved electronic properties and are potential soft materials for organic electronic devices, particularly in bulk heterojunction solar cells. Described herein is how molecular self-assembly, which was originally proposed as a simple laboratory curiosity, has helped the evolution of a variety of soft functional materials useful for advanced electronic devices such as organic field-effect transistors and organic solar cells. Highlights on some of the recent developments are discussed.     

Electrochemistry of Electrode Materials Containing S−Se Bonds for Rechargeable Batteries

Sulfur (S) and selenium (Se) have been considered as promising high capacity cathode materials for rechargeable batteries. They have differences in their physical properties (e.g., electronic conductivity) but the same number of electrons in their outermost shells, which leads to similarity in their electrochemical behavior in batteries. In recent years, some efforts have been taken to combine them in electrodes in the hope of improved battery performance. The S−Se bonds of these electrode materials lead to unusual properties and intriguing electrochemical behavior, which have attracted increasing interest. In this Minireview, electrode materials containing S−Se bonds are summarized, including inorganic S_xSe_y solid solutions, organic compounds, and organic–inorganic hybrid materials. Our understanding in these materials is still premature, but they have shown unique properties to be electrode materials. We hope this Minireview could provide a new insight into the design, synthesis, and understanding of these materials, which could enable high energy density rechargeable batteries.     

A Facile and Efficient Synthesis of Arylsulfonates and Arylsulfonyl Hydrazides under Solvent Free Conditions

Organosulfur compounds are useful materials and most of them have pharmacological properties. The sulfonic esters are important intermediates in organic synthesis and used as acaricides and thermal recording materials. The sulfonyl hydrazides are valuable as inhibitors, agrochemical fungicides, insecticides and photographic images. Some methods have been reported for preparing these compounds to date. Usually, these reactions were carried out in organic solvent[1,2]such as pyridine and DMF. Even up-to date solid-phase synthesis requires solvent. What's more, they have other drawbacks including long reaction time, producing much wastes and by-products, tedious experimental procedure.     

Functional Organic Semiconductors Based on Bay‐Annulated Indigo (BAI)

The advancement of organic electronics has been continually pushed by the need for stable and high performance acceptor materials. By utilizing inexpensive and stable indigo dye as a starting material, Bay‐Annulated Indigo (BAI) provides a new motif for the development of semiconducting materials. Modular and straightforward synthesis makes BAI an outstanding platform for molecular design, while excellent stability, strong absorption, and high ambipolar mobility render BAI‐based materials excellent candidates for organic electronics. BAI‐based polymers and small molecules have taken advantage of these properties to show promising results in a variety of applications.     

Reactions of indole derivatives with cardioprotective activity with reactive oxygen species. Comparison with melatonin

We have previously reported on the synthesis of novel indole derivatives containing an amine-triazole moiety (1a-d, 2a-c), and their antioxidant activity on in vitro non-enzymatic rat hepatic microsomal lipid peroxidation. Some of the compounds showed protective activity against oxidative injury of ischemic myocardium. In the present paper we investigated the interactions of these derivatives with reactive oxygen species, in order to find a mechanism of their antioxidant capacity and to identify structural characteristics responsible for these properties. These interactions were compared with melatonin, which is also an indole derivative. The antioxidant profiles of the compounds were established by different in vitro protocols as follows: 1) by the interaction of the compounds with the 1,1-diphenyl-2-picrylhydrazyl (DPPH) stable free radical, 2) their scavenging effects on superoxide anions using an enzymic system of xanthine-xanthine oxidase, 3) their inhibitory effects on xanthine oxidase and 4) their ability to scavenge hydroxyl radicals by comparison with dimethyl sulfoxide (DMSO) for *OH. All compounds were found to interact with DPPH, most of them to be superoxide anion scavengers and to be strong hydroxyl radical scavengers. Derivatives 1a and 1d substituted on the nitrogen of the indolic nucleus were found to have better antioxidant properties than the reference compounds used and melatonin.     

Chemical and rheological investigations of the sol-gel transition in organically-modified siloxanes

Ormosils are well-known organic-inorganic sol-gel derived materials also called heteropolysiloxanes. This paper presents two basic heteropolysiloxane structures where the organic part is either a short organic chain bridging two silicon atoms for the first material or an organic polymer backbone for the second. Their synthesis is detailed and a variety of experimental techniques (IR, ¹³C and ²⁹Si NMR and CP-MAS NMR, GPC) have been employed to investigate the chemical structure of these new materials. Their mechanical properties, more precisely their viscoelastic behaviour, have been evaluated using dynamic rheological techniques. The storage and loss moduli have been followed during the sol-gel transition at fixed and variable oscillation frequencies. The results have been correlated to the ²⁹Si CP-MAS NMR informations concerning the network polycondensation and compared to a pure inorganic sol-gel material prepared from tetraethoxysilane.     

Silica-based mesoporous organic-inorganic hybrid materials

Mesoporous organic-inorganic hybrid materials, a new class of materials characterized by large specific surface areas and pore sizes between 2 and 15 nm, have been obtained through the coupling of inorganic and organic components by template synthesis. The incorporation of functionalities can be achieved in three ways: by subsequent attachment of organic components onto a pure silica matrix (grafting), by simultaneous reaction of condensable inorganic silica species and silylated organic compounds (co-condensation, one-pot synthesis), and by the use of bissilylated organic precursors that lead to periodic mesoporous organosilicas (PMOs). This Review gives an overview of the preparation, properties, and potential applications of these materials in the areas of catalysis, sorption, chromatography, and the construction of systems for controlled release of active compounds, as well as molecular switches, with the main focus being on PMOs.     

Giant metal-organic frameworks with bulky scaffolds: from microporous to mesoporous functional materials

New concepts on the design and synthesis of crystalline metal-organic frameworks (MOFs) have made them a subject of considerable interest in the growing field of materials science. By creating larger cavity sizes by a nearly infinite combination of metal nodes and organic linkers, many innovative characteristics of microporous MOFs have been revealed. The primary goal of this perspective article is to highlight the frontiers in the development of giant MOFs that are deliberately constructed from metallated or metal-free bulky scaffolds. Incorporating these types of distinct bulky ligands into giant MOFs may lead to MOFs with a large cavity size, intriguing properties and new framework topology. Emerging applications of these materials in catalysis, adsorption, and sensors are also discussed.     

Chemical synthesis of hybrid materials based on PAni and PEDOT with polyoxometalates for electrochemical supercapacitors

Hybrid organic–inorganic materials based on conjugated polymers constitute state-of-the-art compounds with recognized technological implications. In the area of energy conversion, production and storage devices, these materials have been applied as electrodes for batteries, supercapacitors, fuel cells or solar cells, among others. Their importance relies on the wide variety of organic and inorganic counterparts that these hybrids can be made of. The properties from each part can be tailored in order to contribute to a final desired characteristic or the combined properties from both. The unique combination of useful properties found in these materials include electronic conductivity (e⁻ or h⁺), ionic transport, reversible electroactivity, electrooptical properties typical of semiconductors as well as electrochromic, pH- and composition-dependent properties, all of them to add to their polymeric nature. This is an excellent basis for the design of hybrid materials in which either of these properties or their combinations work to enhance or combine with those of a myriad inorganic phases with electronic, magnetic, photochemical, electrochemical, optical or catalytic properties. A large variety of functional hybrid materials can thus be designed and fabricated in which multifunctionality can be easily built to address specific technological needs. In this work we present our most recent results on new synthesis methodology developed for the chemical synthesis of the hybrid PAni/PMo12 and their application as electrochemical supercapacitors. We also report the synthesis of a new hybrid material of PEDOT/PMo12 synthesized for the first time by chemical methods and applied also in electrochemical supercapacitors. Initial results shows capacitance values as high as 168 F/g for the hybrid PAni/PMo12 and about 130 F/g for the hybrid PEDOT/PMo12.     

Hybrid Organic–Inorganic Thermoelectric Materials and Devices

Hybrid organic–inorganic materials have been considered as a new candidate in the field of thermoelectric materials since the last decade owing to their great potential to enhance the thermoelectric performance by utilizing the low thermal conductivity of organic materials and the high Seebeck coefficient, and high electrical conductivity of inorganic materials. Herein, we provide an overview of interfacial engineering in the synthesis of various organic–inorganic thermoelectric hybrid materials, along with the dimensional design for tuning their thermoelectric properties. Interfacial effects are examined in terms of nanostructures, physical properties, and chemical doping between the inorganic and organic components. Several key factors which dictate the thermoelectric efficiency and performance of various electronic devices are also discussed, such as the thermal conductivity, electric transportation, electronic band structures, and band convergence of the hybrid materials.     

Sol–gel derived organic–inorganic hybrid materials: synthesis,characterizations and applications

Organic/inorganic hybrid materials prepared by the sol–gel approach have rapidly become a fascinating new field of research in materials science. The explosion of activity in this area in the past decade has made tremendous progress in both the fundamental understanding of the sol–gel process and the development and applications of new organic/inorganic hybrid materials. Polymer-inorganic nanocomposite present an interesting approach to improve the separation properties of polymer material because they possess properties of both organic and inorganic such as good permeability, selectivity, mechanical strength, and thermal and chemical stability. Composite material derived by combining the sol–gel approach and organic polymers synthesis of hybrid material were the focus area of review It has also been demonstrated in this review that a more complete understanding of their structure–property behavior can be gained by employing many of the standard tools that are utilized for developing similar structure–property relationships of organic polymers. This review article is introductory in nature and gives introduction to composite materials/nanocomposite, their applications and the methods commonly employed for their synthesis and characterization. A brief literature survey on the polysaccharide templated and polysaccharide/protein dual templated synthesis of silica composite materials is also presented in this review article.     

Pyrylogens: synthesis, structural, electrochemical, and photophysical characterization of a new class of electron transfer sensitizers

The synthesis and photophysical properties of a new series of dicationic electron transfer sensitizers have been reported. These new materials, pyrylogens, are hybrids of pyrylium cations and Viologen dications. Electron transfer reactions of neutral organic substrates using these new sensitizers generate radical-cation/radical-cation pairs whose repulsive (repellent) interaction is designed to compete with energy wasting return electron transfer (RET) by enhancing diffusive separation and formation of solvent separated ions.     

Novel hybrid materials consisting of regioregular poly(3-octylthiophene)s covalently attached to single-wall carbon nanotubes

Facile routes for the synthesis of hybrid materials consisting of regioregular poly(3-octylthiophene)s covalently attached to single-wall carbon nanotubes are presented for the first time. These materials are easily processable using common organic solvents, and at the same time combine the properties of regioregular poly(3-alkylthiophene)s with those of single-wall carbon nanotubes. Moreover, studies of the properties of these materials have provided strong evidence for an electron transfer from the regioregular poly(3-octylthiophene) to the single-wall carbon nanotube.