系统研究溶剂和温度对形成三种钴簇基金属-有机框架化合物的影响:结构和气体吸附性质(英文)

Systematic Investigation of the Influences of Solvent and Temperature on the Formation of Three Co-Cluster-Based Metal-Organic Frameworks:Structures and Gas Adsorption Properties

通过调控DMSO/DMF/H2O混合溶剂中溶剂成分的物质的量比和反应温度,合成出3种基于1,3,5-三(4′-羧甲基苯基)苯(H3BTB)和氯化钴的钴簇基金属-有机框架化合物(NH2Me2)2[Co3O(BTB)2(H2O)].2H2O.4.5DMF.7.5DMSO(1),(NH2Me2)2[Co4O(BTB)8/3].6H2O.13DMSO(2)和(NH2Me2)2[Co6O3(BTB)8/3(H2O)4].5H2O.5DMF.13DMSO(3),它们分别含有三核Co3O簇、四核Co4O簇和六核Co6O3簇。这种六核簇为我们首次发现。研究表明,相对中等的温度105℃和较多DMF的使用有利于三核簇的形成;125℃高温和溶剂DMSO有利于四核簇的构建;与形成1的条件相比,较低的温度95℃和更多水的存在则有利于六核簇的生成。2和3虽然由不同的金属簇构成,但具有相同的框架结构,Schlfli符号为(43)8(48.64.812.104)3。此外,还研究了2和3抽出溶剂后产物的气体吸附性质,它们均具有较高的氢气吸附焓。

By controlling the molar ratio of solvent compositions in DMSO/DMF/H2O solvent and reaction temperature,three Co-cluster-based metal-organic frameworks,（NH2Me2）2[Co3O（BTB）2（H2O）].2H2O.4.5DMF.7.5DMSO（1）,（NH2Me2）2[Co4O（BTB）8/3].6H2O.13DMSO（2） and（NH2Me2）2[Co6O3（BTB）8/3（H2O）4].5H2O.5DMF.13DMSO（3）,（BTB,4,4′,4″-benzene-1,3,5-triyl-tribenzoate）,have been synthesized based on H3BTB and cobalt chloride,containing trinuclear Co3O,tetranuclear Co4O and hexanuclear Co6O3 cluster,respectively.The hexanuclear Co-O cluster is observed unprecedentedly.Systematic researches indicate that relatively moderate temperature,105 ℃,and more DMF used could facilitate the formation of trinuclear cluster while high temperature,125 ℃,and DMSO solvent may be in favor of the construction of tetranuclear cluster.However,lower temperature,95 ℃,and more water may contribute to the generation of hexanuclear cluster.In addition,the transformation of 1 to 3 in mother liquid happened when exposed in atmosphere at room temperature.Interestingly,2 and 3 exhibit the identical framework with topological type of the and the Schlfli symbol of（43）8（48.64.812.104）3.Furthermore,the adsorptionproperties of the evacuated products of 2 and 3 have been investigated and both of them have relatively high H2 adsorption enthalpy.