Single-Crystal to Single-Crystal Structural Transformations of Amino-Acid-Based Coordination Polymers: Syntheses and Structural Characterization

T. Tseng, Tzuoo‐Tsair Luo, Hsiao-shan Chiu, Chih‐Chieh Wang, Gene-Hsiang Lee, H. Sheu, Kuang‐Lieh Lu
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Abstract

A discrete complex [Zn(tpro)2(H2O)2] (1, Htpro = L-thioproline), and two structural isomers of coordination polymers, a 1D chain of [Zn(tpro)2]n (2) and a layer structure of [Zn(tpro)2]n (3), have been synthesized and characterized. The discrete complex 1 undergoes a single-crystal to single-crystal temperature-driven structural transformation, leading to a 1D helical coordination polymer 2. Compound 3 has a 2D homochiral layer network with a (4,4) topology. These layers are mutually linked through hydrogen bonding interactions, resulting in the formation of a 3D network. When 1 was heated, it undergoes almost completely conversion to the microcrystalline of compound 2, which was confirmed by powder X-ray diffractions (PXRD). After removing the coordinated water molecules by heating at temperature of up to 150 C, the carboxylate motifs could be activated and their orientations became distorted, after which, they attacked the activation sites of the Zn(II) centers, leading to a the formation of a 1D helix. Moreover, a portion of the PXRD pattern of 3 was converted into a pattern for 2, and the ratio between 2 and 3 was precisely determined by the simulating study of the synchrotron in situ PXRD patterns. Consequently, such a 0D complex is capable of underdoing single-crystal to single-crystal transformations and can be converted into 1D and/or 2D amino acid-based coordination polymers. Prime Archives in Polymer Technology www.videleaf.com
氨基酸基配位聚合物的单晶到单晶结构转变:合成和结构表征
合成了离散配合物[Zn(tpro)2(H2O)2] (1, Htpro = l -硫脯氨酸)和配位聚合物的两种结构异构体[Zn(tpro)2]n(2)的一维链和[Zn(tpro)2]n(3)的层状结构。离散配合物1经历单晶到单晶的温度驱动结构转变,形成一维螺旋配位聚合物2。化合物3具有具有(4,4)拓扑结构的二维同手性层网络。这些层通过氢键相互作用相互连接,形成一个三维网络。当1被加热时,它几乎完全转化为化合物2的微晶,通过粉末x射线衍射(PXRD)证实了这一点。在高达150℃的温度下加热去除配位水分子后,羧酸基序被激活,其取向发生扭曲,攻击Zn(II)中心的活化位点,形成一维螺旋结构。此外,通过对同步加速器原位PXRD谱图的模拟研究,将部分3的PXRD谱图转化为2的PXRD谱图,并精确确定了2与3的比值。因此,这种0D配合物能够进行单晶到单晶的转化,并且可以转化为一维和/或二维氨基酸基配位聚合物。高分子技术主要档案www.videleaf.com
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