两种手性微孔金属有机框架的结构、发光及吸附特性

Structure, luminescence, and adsorption properties of two chiral microporous metal-organic frameworks.

作者信息

Fang Qianrong, Zhu Guangshan, Xue Ming, Sun Jinyu, Sun Fuxing, Qiu Shilun

机构信息

State Key Lab of Inorganic Synthesis & Preparative Chemistry, Jilin University, Changchun 130012, People's Republic of China.

出版信息

Inorg Chem. 2006 May 1;45(9):3582-7. doi: 10.1021/ic051810k.

DOI:10.1021/ic051810k

PMID:16634588

Abstract

Two 3D chiral multifunctional microporous MOFs, Zn3(BTC)2(DMF)3(H2O).(DMF)(H2O) (1) and Cd(4)(BTC)3(DMF)2(H2O)2.6(H2O) (2) (H(3)BTC = 1,3,5-benzenetricarboxylic acid and DMF = N,N'-dimethylformamide), have been synthesized in the presence of organic bases tributylamine (TBA) and triethylamine (TEA), respectively. 1 (C(30)H(38)N(4)O(18)Zn(3)) crystallizes in the tetragonal P4(1)2(1)2 space group (a = 13.6929(19) A, c = 50.664(10) A, V = 9499(3) A(3), and Z = 8). 2 (C33H39N2O28Cd4) crystallizes in the tetragonal P4(3)22 space group (a = 10.3503(4) A, c = 52.557(3) A, V = 5630.4(4) A(3), and Z = 4). X-ray crystallography reveals that 1 consists of a 3D open framework with the (6(3))(4)(6(2).8(2).10(2))(6.(4)8(2))(2) topology, but 2 exhibits a 3D open network with the (4(2).5)(2)(4.(4)5.(10)6.(8)7.(4)8(2)) topology. The solid-state excitation-emission spectra show that the strongest excitation peaks for 1 and 2 are at 341 and 319 nm, and their emission spectra mainly show strong peaks at 410 and 405 nm, respectively. The amounts adsorbed of 1 (2) are 169 mg/g (126 mg/g) for H2O, 137 mg/g (102 mg/g) for C2H5OH, and 133 mg/g (99 mg/g) for CH3OH, which are equivalent to the adsorption of about 62 (34) H2O, 20 (11) C2H5OH, and 28 (16) CH3OH per unit cell, respectively.

摘要

两种三维手性多功能微孔金属有机框架化合物，Zn3(BTC)2(DMF)3(H2O)·(DMF)(H2O) (1) 和Cd(4)(BTC)3(DMF)2(H2O)2·6(H2O) (2)（H(3)BTC = 1,3,5 - 苯三甲酸，DMF = N,N'-二甲基甲酰胺），已分别在有机碱三丁胺（TBA）和三乙胺（TEA）存在的情况下合成。1（C(30)H(38)N(4)O(18)Zn(3)）结晶于四方晶系P4(1)2(1)2空间群（a = 13.6929(19) Å，c = 50.664(10) Å，V = 9499(3) Å(3)，Z = 8）。2（C33H39N2O28Cd4）结晶于四方晶系P4(3)22空间群（a = 10.3503(4) Å，c = 52.557(3) Å，V = 5630.4(4) Å(3)，Z = 4）。X射线晶体学表明，1由具有(6(3))(4)(6(2).8(2).10(2))(6.(4)8(2))(2)拓扑结构的三维开放框架组成，而2呈现出具有(4(2).5)(2)(4.(4)5.(10)6.(8)7.(4)8(2))拓扑结构的三维开放网络。固态激发 - 发射光谱表明，1和2的最强激发峰分别位于341和319 nm，其发射光谱主要分别在410和405 nm处呈现强峰。1（2）对水的吸附量分别为169 mg/g（126 mg/g），对乙醇的吸附量为137 mg/g（102 mg/g），对甲醇的吸附量为133 mg/g（99 mg/g），分别相当于每个晶胞吸附约62（34）个水分子、20（11）个乙醇分子和28（16）个甲醇分子。