Janus-Type Mixed-Valent Copper-Cyanido Honeycomb Layers.

The synthesis of Janus-type layers, which possess front and back sides that consist of different structures, remains a major challenge in the field of two-dimensional materials. In this study, two Janus-type layered coordination polymers, namely, CuII(NEtH2)(NMe2H·H2O)CuI(CN)3 (1) and CuII(NMe2H)(NMe2H·H2O)CuI(CN)3 (2), were synthesized via a simple one-pot procedure using copper(II) nitrate and sodium cyanido in mixed solutions of dimethylamine and ethylamine. Uniquely, 1 and 2 were composed of cyanido-bridged neutral layers and exhibited a CuICuII mixed-valent state. Meanwhile, using a solution of pure dimethylamine for the synthesis yielded the monovalent three-dimensional framework (NMe2H2)[CuI2(CN)3] (3). Results indicated that the simultaneous use of two mixed amines gave rise to the controlled reduction of CuII ions during the reaction. In addition, each face of the layers was coordinated by different amines on the axial positions of the CuII sites, resulting in anisotropic Janus layers. Furthermore, the thermal expansion behavior of 2 was investigated, demonstrating that the neutral [CuICuII(CN)3] layer was relatively rigid compared with the analogous anionic [CuI2(CN)3]- layer.