One-Dimensional Collective Electronic Effects in the Helically Stacked Cs<sub>2</sub>[Ni(CN)<sub>4</sub>]·H<sub>2</sub>O and Cs<sub>2</sub>[Pt(CN)<sub>4</sub>]·H<sub>2</sub>O: X-ray Structure, Polarized Specular Reflectance, and ZINDO Calculations
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The X-ray structure of Cs2[Ni(CN)4]·H2O and the polarized single-crystal UV absorbance spectra of Cs2[Ni(CN)4]·H2O and Cs2[Pt(CN)4]·H2O are presented. The two complexes are isostructural, with helical arrangements of M(CN)42- ions in which there is moderate metal−metal electronic perturbation resulting in a spectral red shift from solution in the UV absorbance spectra. In addition, we have modeled the nickel system with a ZINDO calculation of a three-molecule segment of the helix and have found remarkably good agreement with experiment, including excellent reproduction of the red shift. Crystal data are as follows: Cs2[Ni(CN)4]·H2O, hexagonal, space group P61, a = 9.5260(10) Å, c = 19.043(2) Å, V = 1496.5(3) Å3, T = 100 K, Z = 6, 4335 observed data, R = 0.016, Rw = 0.034.
