Four-step spin-crossover in an oxamide-decorated metal-organic framework
2021
Abstract Spin-crossover (SCO) complexes with multiple spin states are promising candidates for high-order magnetic storage and multiple switches. Here, by employing the N,Nʹ-4-dipyridyloxalamide (dpo) ligand, we synthesize two Hofmann-type metal-organic frameworks (MOFs) [Fe(dpo){Ag(CN)2}2]·3DMF (1) and [Fe(dpo){Ag(CN)2}2]·0.5MeCN·2DEF (2), which exhibit guest dependent four-step SCO behaviors with the sequences of LS → ∼LS2/3HS1/3 → LS1/2HS1/2 → ∼LS3/10HS7/10 → HS and LS → ∼LS2/3HS1/3 → LS1/2HS1/2 → ∼LS1/4HS3/4 → HS, respectively. Therefore, the incorporation of hydrogen-donating/hydrogen-accepting groups into the Hofmann-type MOFs may effectively explore the multi-step SCO materials by tuning hydrogen-bonding interactions.
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