MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Chem Asian J. 2010 Nov 2;5(11):2358-68. doi: 10.1002/asia.201000218.
Assembly of copper(I) halide with a new tripodal ligand, benzene-1,3,5-triyl triisonicotinate (BTTP4), afforded two porous metal-organic frameworks, [Cu(2)I(2)(BTTP4)]⊃2CH(3)CN (1·2CH(3)CN) and [CuBr(BTTP4)]⊃(CH(3)CN·CHCl(3)·H(2)O) (2·solvents), which have been characterized by IR spectroscopy, thermogravimetry (TG), single-crystal, and powder X-ray diffraction (PXRD) methods. Compound 1 is a polycatenated 3D framework that consists of 2D (6,3) networks through inclined catenation, whereas 2 is a doubly interpenetrated 3D framework possessing the ThSi(2)-type (ths) (10,3)-b topology. Both frameworks contain 1D channels of effective sizes 9×12 and 10×10 Å(2), which amounts to 43 and 40% space volume accessible for solvent molecules, respectively. The TG and variable-temperature PXRD studies indicated that the frameworks can be completely evacuated while retaining the permanent porosity, which was further verified by measurement of the desolvated complex [Cu(2)I(2)(BTTP4)] (1'). The subsequent guest-exchange study on the solvent-free framework revealed that various solvent molecules can be adsorbed through a single-crystal-to-single-crystal manner, thus giving rise to the guest-captured structures [Cu(2)I(2)(BTTP4)]⊃C(6)H(6) (1·benzene), [Cu(2)I(2)(BTTP4)]⊃2C(7)H(8) (1·2 toluene), and [Cu(2)I(2)(BTTP4)]⊃2C(8)H(10) (1·2 ethylbenzene). The gas-adsorption investigation disclosed that two kinds of frameworks exhibited comparable CO(2) storage capacity (86-111 mL g(-1) at 1 atm) but nearly none for N(2) and H(2), thereby implying its separation ability of CO(2) over N(2) and H(2). The vapor-adsorption study revealed the preferential inclusion of aromatic guests over nonaromatic solvents by the empty framework, which is indicative of selectivity toward benzene over cyclohexane.
铜（I）卤化物与新型三脚架配体苯-1,3,5-三羧酸三异烟酸（BTTP4）的组装得到了两种多孔金属-有机骨架，[Cu(2)I(2)(BTTP4)]⊃2CH(3)CN(1·2CH(3)CN)和[CuBr(BTTP4)]⊃(CH(3)CN·CHCl(3)·H(2)O)(2·溶剂)，它们已通过红外光谱、热重分析（TG）、单晶和粉末 X 射线衍射（PXRD）方法进行了表征。化合物 1 是一个多连锁的 3D 骨架，由通过倾斜连锁形成的 2D(6,3)网络组成，而 2 是一个双重互穿的 3D 骨架，具有 ThSi(2)-型（ths）(10,3)-b 拓扑结构。这两个骨架都包含 1D 通道，有效尺寸分别为 9×12 和 10×10Å(2)，分别对应溶剂分子的可进入空间体积为 43%和 40%。TG 和变温 PXRD 研究表明，骨架在保留永久孔隙率的情况下可以完全抽空，这通过测量无溶剂配合物[Cu(2)I(2)(BTTP4)]（1'）得到了进一步验证。对无溶剂骨架的后续客体交换研究表明，各种溶剂分子可以通过单晶到单晶的方式被吸附，从而产生捕获客体的结构[Cu(2)I(2)(BTTP4)]⊃C(6)H(6)（1·苯）、[Cu(2)I(2)(BTTP4)]⊃2C(7)H(8)（1·2 甲苯）和[Cu(2)I(2)(BTTP4)]⊃2C(8)H(10)（1·2 乙基苯）。气体吸附研究表明，两种骨架对 CO(2)的存储能力相当（1atm 下为 86-111mL g(-1)），但对 N(2)和 H(2)几乎没有，因此表明其对 CO(2)与 N(2)和 H(2)的分离能力。蒸气吸附研究表明，空骨架优先包含芳香族客体而非非芳香族溶剂，这表明其对苯的选择性高于环己烷。
