Cleaving the framework of CuX with a tetrapyrazolyl-based ligand to construct [CuX]n-based coordination polymers

Abstract

Reactions of CuX (X = Cl, Br, I, SCN, CN) with 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazole)propane (tdmpp) gave rise to five coordination polymers, [{Cu₂X₂(tdmpp)}·Sol]_n (1: X = Cl, Sol = 0.5MeCN; 2: X = Br, Sol = 0.5MeCN; 3: X = I, Sol = MeCN; 4: X = SCN), and [Cu₃(CN)₃(tdmpp)]_n (5). Compounds 1–5 were characterized by elemental analysis, IR, and single crystal X-ray diffraction. Compounds 1–4 contain a 1D helical (1–3) or linear (4) chain assembled by [CuX]₂ cores and tdmpp ligands. While for 5, the zigzag [CuCN]_n chain is linked by tdmpp ligands to form a 2D (4,4) staircase network. The oxidation state of copper in these coordination networks is assumed to be +1. The solid state luminescent properties of compounds 1–5 at ambient temperature were also investigated.