Spin-state ordering in hydroxo-bridged Diiron(III)bisporphyrin complexes

• Verfasst von: Sainna, Mala A. [VerfasserIn]
• Verfasst von: Sil, Debangsu [VerfasserIn]
• Verfasst von: Sahoo, Dipankar [VerfasserIn]
• Verfasst von: Martin, Bodo [VerfasserIn]
• Verfasst von: Rath, Sankar Prasad [VerfasserIn]
• Verfasst von: Comba, Peter [VerfasserIn]
• Verfasst von: Visser, Sam P. de [VerfasserIn]
• Titel: Spin-state ordering in hydroxo-bridged Diiron(III)bisporphyrin complexes
• Verf.angabe: Mala A. Sainna, Debangsu Sil, Dipankar Sahoo, Bodo Martin, Sankar Prasad Rath, Peter Comba, and Sam P. de Visser
• E-Jahr: 2015
• Jahr: January 22, 2015
• Umfang: 12 S.
• Illustrationen: Illustrationen, Diagramme
• Fussnoten: Gesehen am 09.07.2020
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2015
• Band/Heft Quelle: 54(2015), 4, Seite 1919-1930
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/ic502803b
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1724098721

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.