Molecular tectonics: High dimensional coordination networks based on methylenecarboxylate-appended tetramercaptothiacalix[4]arene in the 1,3-alternate conformation

Abstract

© 2018 The Royal Society of Chemistry. The combination, under mild conditions, of the methylenecarboxylic-appended tetramercaptotetrathiacalix[4]arene (TMTCA) derivative 4, blocked in the 1,3-alternate conformation, with acetate salts of octahedral copper(ii), manganese(ii), nickel(ii) and zinc(ii) leads to the formation, in the crystalline state, of high dimensional coordination networks. Depending on the nature of the used metal cations and bases (pyridine or non-coordinating Et3N), six new different high-dimensional coordination polymers have been evidenced, presenting 4 different coordination patterns. All the compounds present a metal/4 ratio equal to 2/1. The formation of a 2D grid-like compound (4-Zn2(Py)4) and three different pseudodiamondoid-like 3D compounds (4-Co2(Py)6(H2O)2, 4-Ni2(Py)6(H2O)2, 4-Mn2(Py)4(MeOH)2, 4-Mn2(DMF)2(MeOH)4 and 4-Zn2(MeOH)4) is observed.