New classes of organic Chelate-Free coordination Polymers: An End-On Azido-Bridged Cu(II) 1-D chain composed of {Cu6(N3)12} repeating units

The use of Me3SiN3 in CuII chemistry, under basic conditions, in the absence of any ancillary organic chelate, has led to an unusual 1-D coordination polymer (1) composed of {Cu6(N3)12} repeating units. The metal ions in 1 are exclusively bridged by mu 3-1,1,1 and mu-1,1 end-on N3- groups. Peripheral ligation about the {Cu6(N3)12} core is provided by eight MeCN solvate molecules. IR and UV/Vis spectroscopic data fully support the presence of endon azides and d-d transitions of the metal ions, respectively. Magnetic susceptibility measurements revealed a continuous drop of the chi\M tau product and an overall antiferromagnetic response, which results in a local S = 0 spin for the {Cu6(N3)12} repeating units of 1. The combined results demonstrate the flexibility of this synthetic approach to purely inorganic-bridged coordination complexes (clusters and polymers) and its ability to yield new molecule-based materials with several potential applications, i.e., in molecular magnetism, catalysis, high energy materials and photochemistry.

Automated summary

The use of Me3SiN3 in CuII chemistry led to the formation of an unusual 1-D coordination polymer composed of {Cu6(N3)12} repeating units, with metal ions bridged exclusively by mu-3-1,1,1 and mu-1,1 end-on N3- groups. Spectroscopic data support the presence of end-on azides and d-d transitions, while magnetic susceptibility measurements revealed an antiferromagnetic response in the repeating units of the polymer. This synthetic approach shows flexibility in generating purely inorganic-bridged coordination complexes and has potential applications in various fields such as molecular magnetism, catalysis, and photochemistry.