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Crystalline arrays of molecular rotors with TIPS-trityl and phenolic-trityl stators using phenylene, 1,2-difluorophenylene and pyridine rotators

机译:带有TIPS-三苯甲基和苯酚-三苯甲基定子的分子转子的晶体阵列,使用亚苯基,1,2-二氟亚苯基和吡啶转子

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摘要

In this work, we describe the synthesis and solid-state characterization of a series of molecular rotors with tri-isopropylsilyloxy-substituted (TIPS) trityl stators axially linked to 1,4-diethynylphenylene, 3,6-diethynyl-1,2-difluorophenylene and 2,5-diethynylpyridine rotators to produce 1,4-bis[(3,3-diphenyl-3-(3'-(tri-isopropylsilyloxy)-phenyl)-prop-1-yn-1-yl)]benzene (1), 1,4-bis[(3,3-diphenyl-3-(3'-(tri-isopropylsilyloxy)-phenyl)-prop-1-yn-1-yl)]-2,3-difluorobenzene (2) and 2,5-bis[(3,3-diphenyl-3-(3'-tri-isopropylsilyloxy)-phenyl)-prop-1-yn-1-yl)]pyridine (3). The subsequent removal of the TIPS protecting group led to their corresponding hydroxyl-substituted trityl derivatives (4) and (5). TIPS- and HO-substituted stators are involved in different inter-and intramolecular interactions (hydrogen bonding, phenyl embraces, C-H-pi interactions) that give rise to isomorphic packing motifs that constrained the rotational dynamics in the solid-state to the slow exchange regime.
机译:在这项工作中,我们描述了一系列轴向与1,4-二乙炔基亚苯基,3,6-二乙炔基-1,2-二氟亚苯基连接的三异丙基甲硅烷基氧基取代(TIPS)三苯甲基定子的分子转子的合成和固态表征和2,5-二甲基吡啶吡啶旋转器生产1,4-双[(3,3-二苯基-3-(3'-(三异丙基甲硅烷氧基)-苯基)-丙-1-炔-1-基)]苯( 1),1,4-双[(3,3-二苯基-3-(3'-(三异丙基甲硅烷氧基)-苯基)-prop-1-yn-1-yl)]-2,3-二氟苯(2 )和2,5-双[(3,3-二苯基-3-(3'-三异丙基甲硅烷氧基)-苯基)-丙-1-炔-1-基)]吡啶(3)。随后除去TIPS保护基,得到它们相应的羟基取代的三苯甲基衍生物(4)和(5)。 TIPS和HO取代的定子参与不同的分子间和分子间相互作用(氢键,苯基环抱,CH-pi相互作用),从而引起同构堆积模体,从而将固态的旋转动力学限制为慢交换机制。

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