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硫杂杯芳烃是一类以硫原子取代桥联亚甲基的新型杯芳烃,作为新一代超分子砌块,在分子识别、超分子自组装、晶体工程和纳米材料等方面都获得了广泛的应用,己成为当今超分子化学研究的新热点. 相似文献
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选择性分离贵金属、放射金属、碱金属等金属离子是重要研究方向之一。硫杂杯芳烃是一类由硫原子桥链苯酚单元构成的大环化合物。作为第三代超分子材料,硫杂杯芳烃反应位点丰富,上边缘、下边缘以及桥链的硫原子上都有进行功能化的可能性,而功能化后硫杂杯芳烃能够表现出与金属离子优异的配位性能,从而达到选择性分离金属离子的目的。本文介绍了硫杂杯芳烃的合成历史、自身结构特点以及配位机理。在此基础上分析了在硫杂杯芳烃的上缘、下缘引入酯基、酰胺、亚胺/胺等官能团后与碱金属、碱土金属、放射金属、贵金属离子等的配位情况,总结了硫杂杯芳烃自身构型、杯环的大小、溶剂类型等对其配位性能的影响,并深入分析了与金属离子的不同配位机理。本文可以为开发高效选择性分离提取各种金属离子的技术提供理论依据。 相似文献
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在过去的几十年里,因其构象及结构上的灵活多变性,使得杯芳烃及其衍生物被作为分子离子识别的载体而引起广泛关注。硫桥杯芳烃是杯芳烃家族的新成员,硫桥的引入使其拥有了许多不同于经典杯芳烃的特点。文章介绍了硫桥杯芳烃的研究进展,其中包括硫桥杯芳烃的特点、母体及其衍生物的合成、分子识别功能及应用。 相似文献
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煤焦油物质丰富、组成复杂,其中,含杂原子的芳香族化合物以及稠环芳烃具有极高的工业应用价值,但是难以通过石化行业获取。如何“破坏”杂原子芳香族化合物和稠环芳烃间的缔合作用,是高效分离的关键和萃取剂选择难点。若对待分离体系中各物质之间的“缔合结构”有清晰的认识,便可根据不同的能量范围设计萃取剂。据此,基于分子力场分析,获得了氮/硫杂原子芳香族化合物色散作用能的范围,约为 -15~-70 kJ/mol,比照分析低共熔溶剂萃取氮/硫杂原子芳香族化合物研究动态,对增强分子间相互作用的调控手段归类,印证了可以根据待分离体系不同的能量范围来选择萃取剂,这种萃取剂选择方法可以作为分离杂原子芳香族化合物和稠环芳烃的一种新策略。 相似文献
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Wang MX 《Accounts of chemical research》2012,45(2):182-195
Pedersen, Lehn, and Cram established supramolecular chemistry through their pioneering work with crown ethers, cryptands, and spherands. Since then, the hallmark of supramolecular science has been an increasing sophistication in the design and construction of macrocyclic molecules, as manifested in cyclodextrin derivatives, calixarenes, resorcinarenes, cyclotriveratrylenes, cucurbiturils, calixpyrroles, cyclophanes, and many other examples. Indeed, macrocyclic compounds provide unique models for the study of noncovalent molecular interactions. They also constitute building blocks for constructing high-level molecular and supramolecular architectures and fabricating molecular devices and advanced materials. As a postgraduate in the Huang laboratory in the late 1980s, I became interested in the calix[n]arenes because of their unique conformational structures and versatile complexation properties. The notion of introducing heteroatoms, and particularly nitrogen, into the bridging position of conventional calixarenes was particularly intriguing. Nitrogen, unlike methylene, can adopt either an sp(2) or sp(3) electronic configuration, providing different conjugation systems with adjacent aromatic rings. Consequently, depending on the configuration and conjugation, a range of C-N bond lengths and C-N-C bond angles is possible. The conformation and cavity size in heteroatom-bridged calixarenes might thus be tuned through the bridging heteroatoms and the number of aromatic rings. Furthermore, because heteroatom linkages significantly affect the electron density and distribution on aromatic rings, the electronic features of macrocyclic cavities might be regulated by heteroatoms. Given the essentially limitless combinations possible, only synthetic hurdles would prevent access to numerous diverse heteracalixaromatics. We began a systematic study on nitrogen- and oxygen-bridged calixarenes in 2000, years later than originally envisioned. Before this study, very few heteracalixaromatics had been reported, owing to the formidable synthetic challenges involved. Apart from thiacalixarene, the synthesis of nitrogen- and oxygen-bridged calixarenes appeared very difficult. But since our first publications in 2004, we have been delighted to see the rapid and tremendous development of the supramolecular chemistry of this new generation of macrocycles. In this Account, I summarize the synthesis of N- and O-bridged calixaromatics and their regiospecific functionalization on the rims and bridging positions, focusing on the fragment coupling approach and contributions from our laboratory. I describe the construction of molecular cages based on heteracalixaromatics and discuss the effect of both bridging heteroatoms and substituents on macrocyclic conformations and cavity sizes. Molecular recognition of neutral organic molecules and charged guest species is also demonstrated. The easy accessibility, rich molecular diversity, unique conformation, and cavity tunability of heteracalixaromatics make them invaluable macrocycles for research in supramolecular chemistry. New heteracalixaromatics, with well-defined conformations and cavity properties, will provide powerful tools for probing noncovalent interactions, leading to the development of new molecular sensing and imaging systems. Multicomponent molecular self-assembly of heteracalixaromatics as functional modules with metals, metal clusters, or charge-neutral species should result in multidimensional solid and soft materials with diverse applications. The profitable incorporation of heteracalixaromatics into molecular devices can also be anticipated in the future. Moreover, the construction of enantiopure, inherently chiral heteracalixaromatics should provide important applications in chiral recognition and asymmetric catalysis. 相似文献
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本文描述了杯芳烃的结构以及它由于此结构而具有的特殊性质。并对杯芳烃的合成作了总结。杯芳烃可以作为相转移催化剂,也可以模拟生物酶并且作为催化剂时有时有立体选择性。本文也对杯芳烃作为各种有机反应的催化剂作了综述。作为相转移催化剂时可以应用在醚合成反应、酯化反应、氧化反应、加成反应、脱水反应、聚合反应和亲核取代反应中,作为模拟酶时可以应用在区域选择催化反应的苯乙烯环氧化反应中。 相似文献
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简要介绍了杯芳烃的结构特征.综述了杯芳烃超分子化合物的组装与聚集、新型杯芳烃大环分子的合成及结构性能、新型杯芳烃的合成组装及选择性识剐作用等方面的研究新进展。 相似文献
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杯芳烃是继环糊精,冠醚之后又一类新兴的大环化合物,以其出色的超分子化学性能日益引起化学,化工界的关注。本文综合近年来的文献报道,介绍了杯芳烃及其衍生物的合成以及目前杯芳烃在诸多工业领域中的应用与发展前景。 相似文献
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简述了杯芳烃的结构特征、特性及应用,较为详细地综述了2010年以来杯芳烃研究的新进展.即:①多种新型杯芳烃的合成;②新型杯芳烃金属配合物的合成;③新型杯芳烃的自组装. 相似文献
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简要介绍了杯芳烃的结构、性能及应用,重点综述了:(1)新型杂原子杯芳烃的合成及超分子自组装;(2)杯芳烃衍生物的合成及对金属离子的识别;(3)杯[4]吡咯席夫碱衍生物的合成。 相似文献
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简要介绍了杯芳烃的结构特征、产生、发展及应用,详细介绍了:①新型杯芳烃的点击合成及应用;②多种系列新型杯芳烃的合成及应用;③新型杯芳烃的合成及其对金属离子的选择性络合作用。并对杯芳烃的发展进行了展望。 相似文献
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