Spin-State Ordering in Hydroxo-Bridged Diiron(III)bisporphyrin Complexes

Sainna, Mala A. ; Sil, Debangsu ; Sahoo, Dipankar ; Martin, Bodo ; Rath, Sankar Prasad ; Comba, Peter ; de Visser, Sam P. (2015) Spin-State Ordering in Hydroxo-Bridged Diiron(III)bisporphyrin Complexes Inorganic Chemistry, 54 (4). pp. 1919-1930. ISSN 0020-1669

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Official URL: http://doi.org/10.1021/ic502803b

Related URL: http://dx.doi.org/10.1021/ic502803b

Abstract

We report the synthesis, structure, and spectroscopic characterization of 1,2-bis[μ-hydroxo iron(III) 5-(2,3,7,8,12,13,17,18-octaethylporphyrinyl)]ethane with PF6– and SbF6– counteranions. The two iron centers are nonequivalent with admixed intermediate spin state (S = 3/2 with a minor contribution of S = 5/2) on each metal both in the solid and in solution. The molecules are compared with previously known μ-hydroxo complexes with other counterions, such as I3–, BF4–, and ClO4–, which demonstrates that the nature of the counterion can affect the spin-state ordering dramatically. To understand how the spin-state ordering is affected by external perturbations, we also have done a comprehensive computational study. The calculations show that subtle environmental perturbations affect the spin-state ordering and relative energies and are likely to be the root cause of the variation in spin-state ordering observed experimentally.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:120893
Deposited On:07 Jul 2021 05:02
Last Modified:07 Jul 2021 05:02

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