The interest in functional supramolecular systems for the design of innovative materials and technologies, able to fundamentally change the world, is growing at a high pace. The huge array of publications that appeared in recent years in the global literature calls for systematization of the structural trends inherent in the formation of these systems revealed at different molecular platforms and practically useful properties they exhibit. The attention is concentrated on the topics related to functional supramolecular systems that are actively explored in institutes and universities of Russia in the last 10–15 years, such as the chemistry of host–guest complexes, crystal engineering, self-assembly and self-organization in solutions and at interfaces, biomimetics and molecular machines and devices.The bibliography includes 1714 references.
After the appearance of the green chemistry concept, which was introduced in the chemistry vocabulary in the early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form the basis for an ideal chemical process. This review analyzes the accumulated experience and achievements towards the design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances. The review presents the views of leading Russian scientists specializing in various fields of this subject, including homogeneous and heterogeneous catalysis, fine and basic organic synthesis, electrochemistry, polymer chemistry, chemistry based on bio-renewable feedstocks and chemistry of energetic compounds and materials. A new approach to the quantitative evaluation of the environmental friendliness of processes developed by Russian authors is described. The bibliography includes 1761.
The present review compiles the advances in the dendritic catalysis within the last two decades, in particular concerning heterogeneous dendrimer-based catalysts and their and application in various processes, such as hydrogenation, oxidation, cross-coupling reactions, etc. There are considered three main approaches to the synthesis of immobilized heterogeneous dendrimer-based catalysts: (1) impregnation/adsorption on silica or carbon carriers; (2) dendrimer covalent grafting to various supports (silica, polystyrene, carbon nanotubes, porous aromatic frameworks, etc.), which may be performed in a divergent (as a gradual dendron growth on the support) or convergent way (as a grafting of whole dendrimer to the support); and (3) dendrimer cross-linking, using transition metal ions (resulting in coordination polymer networks) or bifunctional organic linkers, whose size, polarity, and rigidity define the properties of the resulted material. Additionally, magnetically separable dendritic catalysts, which can be synthesized using the three above-mentioned approaches, are also considered. Dendritic catalysts, synthesized in such ways, can be stored as powders and be easily separated from the reaction medium by filtration/centrifugation as traditional heterogeneous catalysts, maintaining efficiency as for homogeneous dendritic catalysts.
New hybrid catalysts based on Ru nanoparticles, encapsulated into poly(propylene imine dendrimers), immobilized into silica pores, were synthesized and examined for the hydrogenation of alkyl-substituted phenols. The corresponding alkyl-substituted cyclohexanols were presented as the major reaction products, while incomplete hydrogenation products appeared to be minor. A competition between the sterical factors of dendrimer-containing carriers and the electronic factors of substrate substituents influenced the hydrogenation rate of the alkyl-substituted phenols. The carrier structure was found to have a significant influence on both the physical and chemical properties of the catalysts and their hydrogenation activity. The synthesized hybrid catalysts appeared to be stable after recycling and could be re-used several times without significant loss of activity.
Bimetallic MnCo catalyst, supported on the mesoporous hierarchical MCM-41/halloysite nanotube composite, was synthesized for the first time and proved its efficacy in the selective oxidation of p-xylene to terephthalic acid under conditions of the AMOCO process. Quantitative yields of terephthalic acid were achieved within 3 h at 200–250 °C, 20 atm. of O2 and at a substrate to the Mn + Co ratio of 4–4.5 times higher than for traditional homogeneous system. The influence of temperature, oxygen, pressure and KBr addition on the catalyst activity was investigated, and the mechanism for the oxidation of p-toluic acid to terephthalic acid, excluding undesirable 4-carboxybenzaldehyde, was proposed.
This paper describes the first example of using porous aromatic frameworks as supports for sulfide catalysts for the hydrogenation of aromatic hydrocarbons. The synthesis of bimetallic Ni-W and Ni-Mo sulfides was performed by in situ decomposition of [(n-Bu)4N]2[Ni(MeS4)2] (Me = W, Mo) complexes, supported on mesoporous aromatic framework with a diamond-like structure. It is shown that the highest naphthalene conversions were achieved in the case of additional sulfidation with sulfur. After the reaction, catalysts were characterized by X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The activity of synthesized catalysts has been studied using naphthalene as a model substrate. The materials used in this study were substantially active in hydrogenation and slightly in hydrocracking of naphthalene.