标题:In Situ Construction of Three Anion-Dependent Cu(I) Coordination Networks as Promising Heterogeneous Catalysts for Azide-Alkyne \"Click\" Reactions
作者:Xu, Zhenghu;Han, Lu-Lu;Zhuang, Gui-Lin;Bai, Jing;Sun, Di
作者机构:[Xu, Z] Key Lab. of Colloid and Interface Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China;[ Han, L. 更多
通讯作者:Sun, D
通讯作者地址:[Sun, D]Shandong Univ, Sch Chem & Chem Engn, Minist Educ, Key Lab Colloid & Interface Chem, Jinan 250100, Peoples R China.
来源:Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics
出版年:2015
卷:54
期:10
页码:4737-4743
DOI:10.1021/acs.inorgchem.5b00110
摘要:Three Cu(I) coordination networks, namely, {[Cu-2(bpz)(2)(CN)X]center dot CH3CN}(n), (X = Cl, 1; I, 3), {[Cu-6(bpz)(6)(CH3CN)(3)(CN)(3)Br]center dot 2OH center dot 14CH(3)CN}(n), (2, bpz = 3,3\',5,5\'-tetramethyl-4,4\'-bipyrazole), were prepared by using solvothermal method. The cyanide ligands in these networks were generated in situ by cleavage of C-C bond of MeCN under solvothermal condition. The structures of these networks are dependent on halogen anions. Complex 1 is a ladderlike structure with mu(2)-CN- as rung and mu(2)-bpz as armrest. The Cl- in 1 is at terminal position but does not extend the one-dimensional (1D) ladder to higher dimensionalities. Complex 2 is a three-dimensional (3D) framework comprised of novel planar [Cu3Br] triangle and single Cu nodes, which are extended by mu(2)-bpz and mu(2)-CN- to form a novel (3,9)-connected gfy network. Density functional theory calculations showed that single-electron delocalization of Br atom induces the plane structure of [Cu3Br]. Complex 3 also possesses a similar ladderlike subunit as in 1, but the I- acts as bidentate bridge to extend the ladder to 3D framework with a four-connected sra topology. The three networks show notable catalytic activity on the click reaction. The compared catalytic results demonstrate that complex 2 possesses the best catalysis performance among three complexes, which is ascribed to the largest solvent-accessible void (porosity: 2 (29.4%) > 1 (25.7%) > 3 (17.6%)) and the more Cu(I) active sites in 2. The present combined structure-property studies provide not only a new synthetic route to obtain a new kind of catalyst for click reaction but also the new insights on catalyst structure-function relationships.
收录类别:SCOPUS;SCIE
WOS核心被引频次:44
Scopus被引频次:49
资源类型:期刊论文
原文链接:https://www.scopus.com/inward/record.uri?eid=2-s2.0-84929624975&doi=10.1021%2facs.inorgchem.5b00110&partnerID=40&md5=95b05a8c8b975dab262d8df6c05bb319
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