Cooperative Guest Inclusion by a Zeolite Analogue Coordination Polymer. Sorption Behavior with Gases and Amine and Group 1 Metal Salts

TLDR: In this article, a 3D open-framework coordination polymeric polygonal poly(pymo-N1,N3)2] poly(n3) was obtained in the presence of ammonium and perchlorate ions and water molecules in the pores.

Abstract: Reaction of CuX2 (X = NO3, Cl, (SO4)1/2) salts and Hpymo·HX (Hpymo = 2-hydroxypyrimidine; X = Cl, NO3) in aqueous amine solutions (amine = NH3, CH3NH2) leads to formation of the poorly crystalline three-dimensional open-framework coordination polymer [Cu(pymo-N1,N3)2]∞ (1). Under the same reaction conditions, but in the presence of amine and group 1 metal salts of single charged voluminous anions, highly crystalline clathrates of the type {[Cu(pymo-N1,N3)2]·(AX)1/3}∞ (1·AX with A = NH4, CH3NH3, Li, K, Rb; X = ClO4, BF4, PF6) are obtained. The X-ray crystal structure of 1·NH4ClO4 reveals that the combination of square-planar Cu2+ ion with 120° bond angles provided by Hpymo generates a three-dimensional porous [Cu(pymo-N1,N3)2]∞ framework with ammonium and perchlorate ions and water molecules included in the pores. 1 possesses a rich host−guest chemistry. Indeed, N2 sorption at 77 K by empty host 1 reveals its microporous nature with a BET surface area of ca. 200 m2 g-1. Hydrated 1 loses water upon heating ...