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基于(6,3)层状拓扑结构的构象性二倍互穿铀酰超分子异构体:结构、发光及离子交换

Conformational 2-Fold Interpenetrated Uranyl Supramolecular Isomers Based on (6,3) Sheet Topology: Structure, Luminescence, and Ion Exchange.

作者信息

Liu Chao, Wang Chao, Sun Zhong-Ming

机构信息

School of Materials Science and Engineering, Research Center of Rare Earth and Inorganic Functional Materials, State Key Laboratory of Elemento-Organic Chemistry and College of Chemistry , Nankai University , Tianjin 300350 , China.

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry , Chinese Academy of Sciences , 5625 Renmin Street , Changchun , Jilin 130022 , China.

出版信息

Inorg Chem. 2018 Dec 17;57(24):15370-15378. doi: 10.1021/acs.inorgchem.8b02696. Epub 2018 Nov 27.

DOI:10.1021/acs.inorgchem.8b02696
PMID:30481012
Abstract

Six new 2-fold interpenetrated uranyl coordination polymers with two distinct types of (6,3)-net layers, (HO)[(UO)(L)]·HO (1), (Hbipy)[(UO)(L)]·HO (2), (Hbib)[(UO)(L)]·HO (3), (Hdib)[(UO)(L)]·HO (4), [Zn(HO)][(UO)(L)]·5HO (5), and (NH)[(UO)(L)]·HO (6), (bipy = 2,2'-bipyridine, bib = 4,4'-di(1 H-imidazol-1-yl)-1,1'-biphenyl, and dib = 1,4-di(1 H-imidazol-1-yl)benzene), were hydrothermally prepared from a tripodal polycarboxylate ligand, tri(4-carboxyphenyl)phenylsilane (HL), with different N-bearing organic templates as the stacking templates and charge compensators. Structural analyses indicate that these compounds comprise two sets of conformational supramolecular isomers because of the same framework compositions but different conformations of the carboxylate ligands. The solid-state emission spectra of compounds 1-6 were recorded. Ion-exchange studies revealed that the ammonia hydrate in 6 can be selectively substituted by alkali metal cations with appropriate ionic radii, and that the resulting structures remain stable, as demonstrated by crystallographic characterization.

摘要

通过水热法,以三脚架多羧酸盐配体三(4-羧基苯基)苯基硅烷(HL)为原料,使用不同的含氮有机模板作为堆积模板和电荷补偿剂,制备了六种新型的具有两种不同类型(6,3)-网状层的二倍穿插铀酰配位聚合物,分别为(HO)[(UO)(L)]·HO(1)、(Hbipy)[(UO)(L)]·HO(2)、(Hbib)[(UO)(L)]·HO(3)、(Hdib)[(UO)(L)]·HO(4)、[Zn(HO)][(UO)(L)]·5HO(5)和(NH)[(UO)(L)]·HO(6)(bipy = 2,2'-联吡啶,bib = 4,4'-二(1H-咪唑-1-基)-1,1'-联苯,dib = 1,4-二(1H-咪唑-1-基)苯)。结构分析表明,由于框架组成相同但羧酸根配体的构象不同,这些化合物包含两组构象超分子异构体。记录了化合物1-6的固态发射光谱。离子交换研究表明,6中的水合氨可以被具有适当离子半径的碱金属阳离子选择性取代,并且所得结构保持稳定,晶体学表征证明了这一点。

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