Mixed-Metal Cu-Zn Thiocyanate Coordination Polymers with Melting Behavior, Glass Transition, and Tunable Electronic Properties

The solid-state mechanochemical reactions under ambient conditions of CuSCN and Zn(SCN)₂ resulted in two novel materials: partially Zn-substituted α-CuSCN and a new phase Cu_xZn_y(SCN)_x+2y. The reactions take place at the labile S-terminal, and both products show melting and glass transition behaviors. The optical band gap and solid-state ionization potential can be adjusted systematically by adjusting the Cu:Zn ratio. Density functional theory calculations also reveal that the Zn-substituted CuSCN structure features a complementary electronic structure of Cu 3d states at the valence band maximum (VBM) and Zn 4s states at the conduction band minimum (CBM). This work shows a new route to develop semiconductors based on coordination polymers which are becoming technologically relevant for electronic and optoelectronic applications.