Iron(II) Complexes of 2,6-Di[4-(ethylcarboxy)pyrazol-1-yl]pyridine with Reversible Guest-Modulated Spin-Crossover Behavior
2023
García López, Víctor | El Mansour El Jastimi, Hanane | Juráková, Jana | Clemente León, Miguel | Coronado Miralles, Eugenio
Three solvatomorphs of the iron(II) complex of 2,6-di[4-(ethylcarboxy)pyrazol-1-yl]pyridine (bpCOOEt2p) of formulas [Fe(bpCOOEt2p)2](ClO4)2·1.5MeNO2 (1), [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2), and [Fe(bpCOOEt2p)2](ClO4)2·2MeNO2 (3) have been prepared and characterized. They show interesting spin-crossover (SCO) properties ranging from partial to complete thermalspin transitions and a light-induced excited spin-state trapping (LIESST) effect. In solvatomorph 2, a robust structure is formed with channels that enable the entrance or removal of solvent molecules by vapor diffusion without losing the crystallinity. Thus, solvent-exchanged samples [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2·MeNO2), [Fe(bpCOOEt2p)2(ClO4)2·MeCN (2·MeCN), [Fe(bpCOOEt2p)2](ClO4)2·0.5Me2CO (2·Me2CO), and [Fe(bpCOOEt2p)2](ClO4)2· MeCOOH (2·MeCOOH) were prepared by vapor diffusion of the solvents in a crystal of the compound previously heated to 400 K in a single-crystal to single-crystal (SCSC) fashion. Interestingly, this causes a change of spin state with a stabilization of the low-spin state in 2·Me2CO and the high-spin state in 2·MeCN. Therefore, the SCO properties of 2 can be tuned in a reversible way by exposure to different solvents.
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