Please use this identifier to cite or link to this item: https://hdl.handle.net/2440/135646
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Type: Journal article
Title: Toward High-Temperature Light-Induced Spin-State Trapping in Spin-Crossover Materials: The Interplay of Collective and Molecular Effects
Author: Nadeem, M.
Cruddas, J.
Ruzzi, G.
Powell, B.J.
Citation: Journal of the American Chemical Society, 2022; 144(20):9138-9148
Publisher: American Chemical Society (ACS)
Issue Date: 2022
ISSN: 0002-7863
1520-5126
Statement of
Responsibility: 
M. Nadeem, Jace Cruddas, Gian Ruzzi, and Benjamin J. Powell
Abstract: Spin-crossover (SCO) materials display many fascinating behaviors including collective phase transitions and spin-state switching controlled by external stimuli, e.g., light and electrical currents. As singlemolecule switches, they have been fêted for numerous practical applications, but these remain largely unrealized−partly because of the difficulty of switching these materials at high temperatures. We introduce a semiempirical microscopic model of SCO materials combining crystal field theory with elastic intermolecular interactions. For realistic parameters, this model reproduces the key experimental results including thermally induced phase transitions, light-induced spin-state trapping (LIESST), and reverse-LIESST. Notably, we reproduce and explain the experimentally observed relationship between the critical temperature of the thermal transition, T1/2, and the highest temperature for which the trapped state is stable, TLIESST, and explain why increasing the stiffness of the coordination sphere increases TLIESST. We propose strategies to design SCO materials with higher TLIESST: optimizing the spin−orbit coupling via heavier atoms (particularly in the inner coordination sphere) and minimizing the enthalpy difference between the high-spin (HS) and low-spin (LS) states. However, the most dramatic increases arise from increasing the cooperativity of the spin-state transition by increasing the rigidity of the crystal. Increased crystal rigidity can also stabilize the HS state to low temperatures on thermal cycling yet leave the LS state stable at high temperatures following, for example, reverse-LIESST. We show that such highly cooperative systems offer a realistic route to robust room-temperature switching, demonstrate this in silico, and discuss material design rationale to realize this.
Rights: Copyright © 2022, American Chemical Society
DOI: 10.1021/jacs.2c03202
Grant ID: http://purl.org/au-research/grants/arc/DP200100305
Appears in Collections:Chemistry publications

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