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Three Coordination Polymers Based on 1H-Tetrazole (HTz) Generated via in Situ Decarboxylation: Synthesis, Structures, and Selective Gas Adsorption Properties

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Di-Chang Zhong†, Wen-Guan Lu‡, Long Jiang†, Xiao-Long Feng† and Tong-Bu Lu*†

^† MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, and School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China

^‡ Department of Chemistry, Shaoguan University, Shaoguan 512005, P. R. China

Cryst. Growth Des., 2010, 10 (2), pp 739–746

DOI: 10.1021/cg901128k

Publication Date (Web): November 24, 2009

*To whom correspondence should be addressed. Fax: +86-20-84112921. E-mail: lutongbu@mail.sysu.edu.cn.

Section:

Inorganic Chemicals and Reactions

Abstract

Three tetrazole-based coordination polymers, [Zn₃(Tz)₆(H₂O)₂]_n (1), [Cu₂(Tz)₃(OH)]_n (2), and {[Cu₅(Tz)₉](NO₃)·8H₂O}_n (3) (Tz = tetrazolate) have been prepared under hydro(solvo)thermal conditions using ethyl tetrazolate-5-carboxylate and corresponding metal salts as building blocks, in which tetrazolate was generated via in situ decarboxylation. The results of X-ray single diffraction analyses indicate that 1 possesses a 2D layer structure with μ₂-Tz⁻ bridged six- and four-coordinated Zn(II), forming a rare kagomé dual topological layer. Compound 2 is a 3D layer−pillar structure, in which the Cu(II) ions are bridged by μ₃-Tz⁻ anions to generate a 2D sheet, and the 2D sheets are further pillared by μ₂-Tz⁻ and μ₂-OH⁻ to form a 3D framework with a fsc topology net. Compound 3 is a 3D porous framework with an acs topology net. Compound 1 exhibits photoluminescent properties with an emission peak at 467 nm, and compound 3 shows selective H₂ and CO₂ over N₂ adsorption.

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