A three-state model for the polymorphism in linear tricobalt compounds.

Journal article

The remarkable polymorphism exhibited by the linear tricobalt compounds, Co3(mu3-dpa)4Cl2 and Co3(mu3-dpa)4Br2, can be explained using a model involving three distinct electronic states. At high temperatures, symmetric and unsymmetric forms arise from the population of doublet (2A) and quartet (4B) states, respectively, the latter containing a localized high-spin Co(II) center. In the unsymmetric form, a reduction in temperature leads to a spin-crossover to a second quite distinct doublet state, 2B, where, uniquely, the d(x2-y2) character on the localized Co(II) center is distributed between the occupied and vacant manifolds. The variable population of the Co d(x2-y2) orbital gives rise to the continuous change in Co-Co and Co-N bond lengths as the temperature is decreased.

Authors: Pantazis, D; McGrady, J

• Publication status: Published
• Journal: Journal of the American Chemical Society
• Volume: 128
• Issue: 12
• Pages: 4128-4135
• Publication date: 2006-03-01
• DOI: 10.1021/ja0581402
• EISSN: 1520-5126
• ISSN: 0002-7863
• Language: English