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Chiral Recognition between Metallohelicates via Strong H Bonds: Homochiral Bishelical Coupling and Mesohelical Polymerization

机译:通过强氢键在金属螺旋化合物之间的手性识别:同手性双分子偶联和介螺旋聚合

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摘要

A rigid, one-dimensional, and monotopic ligand containing both a proton donor and a proton acceptor, 2-[(1Himidazol-2-yl)methyleneamino]phenol (H2L), has been used to attain three hierarchically assembled supramolecular polymers. The handedness of these hydrogen-bonded metallo-supramolecular structures is modulated by a selective coupling, via strong H bonds with significant covalent character. Thus, alternate Delta and A enantiomers of Cd(HL)(2) form a one-dimensional supramolecular polymer via mutual strong N-H center dot center dot center dot O interactions (2.58 angstrom), which are associated with a hydrogen bond energy value of similar to 11.5 kcal mol(-1). In contrast, homochiral self-recognition of enantiomers of M(HL)(2) and [M(H2L)(2)](2+) (M = Cu-II and Ni-II) gives rise to dinuclear bishelicates, whose metallohelical units are held together by two strong O-H center dot center dot center dot O bonds (2.41-2.44 angstrom), which are associated with hydrogen bond energies in the range of 25-35 kcal mol(-1).
机译:包含质子供体和质子受体2-[((1Himidazol-2-基)亚甲基氨基]苯酚(H2L)的刚性,一维单峰配体已用于获得三种层次组装的超分子聚合物。这些氢键键合的金属-超分子结构的旋向性通过具有显着共价特征的强H键通过选择性偶合来调节。因此,Cd(HL)(2)的交替Delta和A对映异构体通过相互较强的NH中心点中心点中心点O相互作用(2.58埃)形成一维超分子聚合物,这与相似的氢键能值相关至11.5 kcal mol(-1)。相反,M(HL)(2)和[M(H2L)(2)](2+)(M = Cu-II和Ni-II)对映异构体的同手性自识别产生双核双酚盐,其金属螺旋单元通过两个强OH中心点中心点中心点O键(2.41-2.44埃)结合在一起,这些键与25-35 kcal mol(-1)范围内的氢键能相关。

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