CunXn]‐Based Coordination Polymers with Bis(4‐iodo‐1H‐pyrazol‐1‐yl)methane and Bis(4‐iodo‐3, 5‐dimethyl‐1H‐pyrazol‐1‐yl)methane: Solvothermal Syntheses, Crystal Structures, and Luminescent Properties

Abstract

AbstractSolvothermal reactions of CuX (X = Cl, Br, I, CN) with bis(4‐iodo‐1H‐pyrazol‐1‐yl)methane (ipzm) or its methyl‐substituted derivative bis(4‐iodo‐3, 5‐dimethyl‐1H‐pyrazol‐1‐yl)methane (idmpzm) resulted in the formation of three 2D [Cu2X2]n‐based coordination polymers [{Cu(μ‐X)}2(μ‐ipzm)]n [X = Cl (1), Br (2), I (3)], four 1D [CuX]n‐based coordination polymers [{Cu(μ‐CN)}2(μ‐ipzm)]n (4), [{(idmpzm)Cu}(μ‐Cl)]n (5), [{(idmpzm)Cu}(μ‐Br)·MeCN]n (6), [{(idmpzm)Cu}(μ‐I)·0.5MeCN]n (7), and one 1D [Cu6(CN)6]n‐based coordination polymer [{Cu(μ‐CN)}6(idmpzm)3]n (8). Compounds 1–8 were characterized by elemental analysis, IR spectra, and single‐crystal X‐ray diffraction. Compounds 1–3 consist of an unique 2D layer structure, in which the 1D staircase [Cu2X2]n chains are linked by ipzm ligands via the μ‐η1(N)‐η1(N) coordination mode. In 4, two 1D zigzag [CuCN]n chains are linked by μ‐ipzm ligands to form a 1D double chain. Compounds 5–7 have a 1D split‐stair chain derived from connecting [Cu(idmpzm)] fragments via μ‐X (X = Cl, Br, I) bridges, whereas 8 exhibits a 1D scolopendra‐like chain assembled from a 1D [Cu6(CN)6]n chain with idmpzm ligands chelating on the outer central CuI atoms. The luminescence properties of 1–8 along with free ipzm and idmpzm ligands at ambient temperature were also investigated.