Effect of Ligand Modulation on Metal-to-Metal Electron Transfer in a Series of Fe2Co2 Molecular Square Complexes

Kamilya, S and Ghosh, S and Mehta, S and Mondal, A (2021) Effect of Ligand Modulation on Metal-to-Metal Electron Transfer in a Series of Fe2Co2 Molecular Square Complexes. In: Journal of Physical Chemistry A, 125 (22). pp. 4775-4783.

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Abstract

A series of three new cyanide-bridged FeCo molecular square complexes, namely, {Fe(Tp*)(CN)32Co(L)22}(BF4)2·2DMF (L = bik (1), bik� (2), and vbik (3); Tp� = hydrotris(3,5-dimethylpyrazol-1-yl)borate, bik = bis(1-methyl-1H-imidazol-2-yl)ketone, bik� = bis(1-ethyl-1H-imidazol-2-yl)ketone, and vbik = bis(1-vinyl-1H-imidazol-2-yl)ketone; DMF = dimethylformamide) were synthesized and characterized by single-crystal X-ray diffraction analyses and by magnetic, electrochemical, and spectroscopic measurements. Magnetic studies reveal that all three complexes exhibit temperature-induced metal-to-metal electron transfer (MMET) from a high-spin Co(II) center to a low-spin Fe(III) center, transforming a high-temperature paramagnetic {FeIIILS-CN-CoIIHS} ground state into a low-temperature diamagnetic {FeIILS-CN-CoIIILS} state with a decrease in the temperature from 300 to 100 K. Complexes 1 and 3 show the interconversion of the paramagnetic {FeIIILS-CN-CoIIHS} ground state into a diamagnetic {FeIILS-CN-CoIIILS} state in a single-step transition with T1/2 values of 180 and 186 K, respectively, while a two-step MMET with T1/2 value of 214 and 178 K was observed for complex 2. ©

Item Type:	Journal Article
Publication:	Journal of Physical Chemistry A
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society
Keywords:	Cobalt compounds; Cobalt metallography; Dimethylformamide; Electron transitions; Electron transport properties; Ground state; Ketones; Metals; Organic solvents; Paramagnetism; Single crystals; Temperature; X ray diffraction analysis, Electron transfer; High temperature; Magnetic studies; Molecular squares; Single crystal X-ray diffraction analysis; Single-step transition; Spectroscopic measurements; Temperature-induced, Iron compounds
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	17 Aug 2021 06:33
Last Modified:	17 Aug 2021 06:33
URI:	http://eprints.iisc.ac.in/id/eprint/69194

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