One-dimensional collective electronic effects in the helically stacked Cs2[Ni(CN)4].H2O and Cs2[Pt(CN)4].H2O: X-ray structure, polarized specular reflectance, and ZINDO calculations

Jeffrey B Cornelius; Robert M Trapp; Terry J Delord; Frank R Fronczek; Steven F Watkins; Jill Jasin Orosz; Ronald L Musselman

doi:10.1021/ic026101a

One-dimensional collective electronic effects in the helically stacked Cs2[Ni(CN)4].H2O and Cs2[Pt(CN)4].H2O: X-ray structure, polarized specular reflectance, and ZINDO calculations

Inorg Chem. 2003 May 5;42(9):3026-35. doi: 10.1021/ic026101a.

Authors

Jeffrey B Cornelius¹, Robert M Trapp, Terry J Delord, Frank R Fronczek, Steven F Watkins, Jill Jasin Orosz, Ronald L Musselman

Affiliation

¹ Department of Chemistry, Principia College, Elsah, Illinois 62028, USA.

PMID: 12716197
DOI: 10.1021/ic026101a

Abstract

The X-ray structure of Cs(2)[Ni(CN)(4)].H(2)O and the polarized single-crystal UV absorbance spectra of Cs(2)[Ni(CN)(4)].H(2)O and Cs(2)[Pt(CN)(4)].H(2)O are presented. The two complexes are isostructural, with helical arrangements of M(CN)(4)(2)(-) 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: Cs(2)[Ni(CN)(4)].H(2)O, hexagonal, space group P6(1), a = 9.5260(10) A, c = 19.043(2) A, V = 1496.5(3) A(3), T = 100 K, Z = 6, 4335 observed data, R = 0.016, R(w) = 0.034.