Two-Step Thermoinduced Metal-to-Metal Electron Transfer and ON/OFF Photoswitching in a Molecular [Fe 2 Co 2 ] Square Complex - Archive ouverte HAL Access content directly
Journal Articles Inorganic Chemistry Year : 2020

Two-Step Thermoinduced Metal-to-Metal Electron Transfer and ON/OFF Photoswitching in a Molecular [Fe 2 Co 2 ] Square Complex

Abstract

A cyanide-bridged [Fe 2 Co 2 ] molecular square complex, {[Fe(Tp)(CN) 3 ] 2 [Co(L) 2 ] 2 }(BF 4) 2 •2CH 3 CN•6H 2 O [1; Tp = hydrotris(pyrazol-1-yl)borate and L = bis(1-ethyl-1Himidazol-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 (T 1/2 ↑ = 332 and 407 K and T 1/2 ↓ = 320 and 405 K, respectively), converting the low-temperature diamagnetic {Fe II LS −CN−Co III LS } ground state into the high-temperature paramagnetic {Fe III LS − CN−Co II HS } 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 (T LIESST = 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, {Fe II LS −CN−Co III LS }, and the paramagnetic state, {Fe III LS −CN−Co II HS }, under the application of temperature and light.
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Dates and versions

hal-03082269 , version 1 (18-12-2020)

Identifiers

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Sujit Kamilya, Subrata Ghosh, Yanling Li, Pierre Dechambenoit, Mathieu Rouzières, et al.. Two-Step Thermoinduced Metal-to-Metal Electron Transfer and ON/OFF Photoswitching in a Molecular [Fe 2 Co 2 ] Square Complex. Inorganic Chemistry, 2020, 59 (17), pp.11879-11888. ⟨10.1021/acs.inorgchem.0c02053⟩. ⟨hal-03082269⟩
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