A luminescent two-dimensional coordination polymer of type [Cd(H2O)(EtOH)][ReN(CN)4(H2O)]¢2H2O (CdRe) incorporating “Janus-type” cyanido-bridged layers was synthesized. Within each layer of CdRe, the asymmetric [ReN(CN)4]21 units are arranged so that all nitrides are oriented in the same direction. Moreover, Cd ions also have an asymmetric coordination structure, with ethanol being bound axially on the nitride side, and water on the opposite side. Layers are then stacked in a head-to-head manner, defining a succession of hydrophilic and hydrophobic interlayer domains. CdRe exhibits anisotropic thermal expansion including in-plane negative and out-of-plane positive thermal expansion behavior, and shows green emission (em = 509 nm) originating from the metal-centered dd transition of [ReN(CN)4]21 units.
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