Abstract
Two layered iodoargentates, [HCP][Ag2I3] (HCP+ = NH-4-cyanopyridinium) (1) and [MCP][Ag4I5] (MCP+ = N-methyl-3-cyanopyridinium) (2) have been solvothermally synthesized. For 1, the inorganic layer is built up by 4-connected Ag4I8 unit with cubane-type Ag4I4 core via sharing peripheral μ2-I in ab plane, while the HCP+ cations are located at the apertures and interlayer space. For 2, the inorganic layer is constructed from [Ag6I6]n and [AgI3]n2n– chains via alternative corner- and edge-sharing modes along the b-axis, while the MCP+ cations lie between neighboring layers. Compounds 1 and 2 exhibit reducing band gaps relative to the bulk β-AgI and remarkable thermochromism, which are ascribed to the intermolecular charge transfer (CT) and affected by electron affinity of pyridinium cations.
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