Two-Step Thermoinduced Metal-to-Metal Electron Transfer and ON/OFF Photoswitching in a Molecular Fe2Co2 Square Complex

Kamilya, S and Ghosh, S and Li, Y and Dechambenoit, P and Rouzières, M and Lescouëzec, R and Mehta, S and Mondal, A (2020) Two-Step Thermoinduced Metal-to-Metal Electron Transfer and ON/OFF Photoswitching in a Molecular Fe2Co2 Square Complex. In: Inorganic Chemistry .

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Abstract

A cyanide-bridged Fe2Co2 molecular square complex, {Fe(Tp)(CN)32Co(L)22}(BF4)2·2CH3CN·6H2O 1; Tp = hydrotris(pyrazol-1-yl)borate and L = bis(1-ethyl-1H-imidazol-2-yl)ketone, has been synthesized and characterized fully by single-crystal X-ray diffraction, (photo)magnetic measurements, optical reflectivity, and other physical measurements. 1 exhibits a two-step metal-to-metal electron-transfer (MMET)-induced spin transition accompanied by thermal hysteresis (T1/2� = 332 and 407 K and T1/2� = 320 and 405 K, respectively), converting the low-temperature diamagnetic {FeIILS-CN-CoIIILS} ground state into the high-temperature paramagnetic {FeIIILS-CN-CoIIHS} state. Additionally, 1 displays reversible photoinduced MMET under light irradiation (ON mode using 808 nm laser light and OFF mode using 532 nm laser light), as confirmed by optical reflectivity and (photo)magnetic measurements. The photoinduced paramagnetic metastable state relaxes back to the diamagnetic ground state at 91 K (TLIESST = 91 K). Astonishingly, 1 also exhibits a 27 K wide light-induced thermal hysteresis below 100 K. The overall results show that 1 is a multistimuli-responsive bistable material that exhibits reversible switching between the diamagnetic state, {FeIILS-CN-CoIIILS}, and the paramagnetic state, {FeIIILS-CN-CoIIHS}, under the application of temperature and light.

Item Type:	Journal Article
Publication:	Inorganic Chemistry
Publisher:	American Chemical Society
Additional Information:	The copyright of this article belongs to American Chemical Society
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	30 Sep 2020 10:03
Last Modified:	30 Sep 2020 10:03
URI:	http://eprints.iisc.ac.in/id/eprint/66655

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