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

Three tetrazole-based coordination polymers, [Zn 3 (Tz) 6 (H 2 O) 2 ] n ( 1 ), [Cu 2 (Tz) 3 (OH)] n ( 2 ), and {[Cu 5 (Tz) 9 ](NO 3 )·8H 2 O} 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 μ 2 -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 μ 3 -Tz − anions to generate a 2D sheet, and the 2D sheets are further pillared by μ 2 -Tz − and μ 2 -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 H 2 and CO 2 over N 2 adsorption.