Toward High-Temperature Light-Induced Spin-State Trapping in Spin-Crossover Materials: The Interplay of Collective and Molecular Effects

旋转交叉 化学 合作性 自旋跃迁 自旋态 相变 凝聚态物理 化学物理 结晶学 物理 无机化学 生物化学
作者
Muhammad Nadeem,Jace Cruddas,Gian Ruzzi,B. J. Powell
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:144 (20): 9138-9148 被引量:6
标识
DOI:10.1021/jacs.2c03202
摘要

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 single-molecule 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.
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