Journal
INORGANIC CHEMISTRY
Volume 59, Issue 17, Pages 11879-11888Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.0c02053
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Funding
- Indian Institute of Science (IISc), Bangalore, India [R(VI)090/1076/2017-515]
- Science & Engineering Research Board [SRG/2019/000317]
- Department of Science and Technology (DST-RFBR)
- Indo Russia Joint Research Funding [INT/RUS/RFBR/373]
- Ministry of Human Resource Development (MHRD), Government of India [SG/MHRD-17-0014, SR/MHRD-17-0011]
- Council of Scientific & Industrial Research, Government of India
- IISc
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A cyanide-bridged [Fe(2)Co2] molecular square complex, {[Fe(Tp)(CN)3]2[Co(L)2]2}(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 {FeCNCo} ground state into the high-temperature paramagnetic {FeCNCo} 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, {FeCNCo}, and the paramagnetic state, {FeCNCo}, under the application of temperature and light.
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