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 and Zn 4s states at the conduction band minimum. This work shows a new route to develop semiconductors based on coordination polymers, which are becoming technologically relevant for electronic and optoelectronic applications.

中文翻译：

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具有熔融行为、玻璃化转变和可调电子特性的混合金属 Cu-Zn 硫氰酸酯配位聚合物

CuSCN 和 Zn(SCN) ₂在环境条件下的固态机械化学反应产生了两种新材料：部分 Zn 取代的 α-CuSCN 和新相 Cu _x Zn _y (SCN) _{x +2 y}. 反应发生在不稳定的 S 端，两种产物都表现出熔融和玻璃化转变行为。可以通过调节 Cu/Zn 比来系统地调节光学带隙和固态电离电位。密度泛函理论计算还表明，Zn 取代的 CuSCN 结构具有价带最大值处的 Cu 3d 态和导带最小值处的 Zn 4s 态的互补电子结构。这项工作展示了开发基于配位聚合物的半导体的新途径，这些聚合物在技术上与电子和光电应用相关。