Construction of heterometallic and mixed-valence copper(I/II) chloride π-complexes with 1,2,4-triazole allyl-derivative

Abstract

Copper(I) coordination compounds with allyl-derivatives of various heterocycles are an interesting subject of current research, however, the possibility of exploiting a second metal cation (i.e. obtaining heterobimetallic complexes) as a tool for crystal engineering of copper(I) π-complexes has been virtually uninvestigated. In this work we report the synthesis, structure, magnetic and non-linear optical properties of a family of heterometallic (CuI – AgI, CuI – ZnII, CuI – FeII) and mixed-valence (CuI – CuII) copper(I) η2-π-complexes with an 3-allylsulfanyl-4-allyl-5-phenyl-4H-1,2,4-triazole (L). The structures of obtained complexes can be considered as consisting of two subunits: cationic organometallic moiety formed by Cu(I) ions, and anionic inorganic fragments. The anionic part, formed by the second metal cation, determines the dimensionality of a crystal structure – it either connects two copper(I) ions in a bridging mode within the organometallic moiety leading to the 0D structure (in the case of CuI – ZnII & CuI – FeII), or links cationic organometallic dimers into the 1D ladder (CuI – AgI & CuI – CuII). Magnetic properties of mixed-valence Cu(I/II) and heterometallic Cu(I)/Fe(II) coordination compounds have been studied and discussed. Separate studies have been done for the laser stimulated nonlinear optics.