Syntheses, Structures, and Properties of Two Three-Dimensional Octacyanometalate-Based Polymers: Cs<sub>2</sub>Cu<sub>3</sub>[W(CN)<sub>8</sub>]<sub>2</sub>·4NH<sub>3</sub>·4H<sub>2</sub>O and Cu<sub>2</sub>[Mo(CN)<sub>8</sub>]·8NH<sub>3</sub>
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The syntheses, X-ray structures, and magnetic properties of two 3D cyano-bridged assemblies, CsI2CuII3[WIV(CN)8]2·4NH3·4H2O (1) and CuII2[MoIV(CN)8]·8NH3 (2), are presented. Both complexes 1 and 2 were synthesized in aqueous ammonia solution, and the crystal growth was dynamically controlled by introducing the competition mechanism between precipitation and coordination reactions. Complexes 1 and 2 crystallize in the monoclinic system and have space group P21/c, but complex 1 has unit cell constants a = 15.0213(17) Å, b = 7.4222(7) Å, c = 15.3083(14) Å, and Z = 2, while complex 2 has a = 13.1877(14) Å, b = 9.1381(10) Å, c = 17.3340(18) Å, and Z = 2. The structure of complex 1 consists of [CuII(NH3)4] and [CuII(H2O)] units bridged by [WIV(CN)8] to form a 3D network, where CsI ions balance the electrovalence to complete the neutral structure with the residual water molecules in the lattice. The structure of complex 2 shows that three CuII(NH3)4 sites are axially connected by [MoIV(CN)8]4- weakly coordinating to CuII ions to lead to a 3D structure. The magnetic investigation exhibits the very weak antiferromagnetic coupling between CuII ions for both of complexes 1 and 2 because of the diamagnetic octacyanometalate bridge.
