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Iron(II) Complexes of 2,6-Di[4-(ethylcarboxy)pyrazol-1-yl]pyridine with Reversible Guest-Modulated Spin-Crossover Behavior.
- Source :
-
Crystal growth & design [Cryst Growth Des] 2023 Mar 02; Vol. 23 (4), pp. 2730-2738. Date of Electronic Publication: 2023 Mar 02 (Print Publication: 2023). - Publication Year :
- 2023
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Abstract
- Three solvatomorphs of the iron(II) complex of 2,6-di[4-(ethylcarboxy)pyrazol-1-yl]pyridine (bpCOOEt <subscript>2</subscript> p) of formulas [Fe(bpCOOEt <subscript>2</subscript> p) <subscript>2</subscript> ](ClO <subscript>4</subscript> ) <subscript>2</subscript> ·1.5MeNO <subscript>2</subscript> ( 1 ), [Fe(bpCOOEt <subscript>2</subscript> p) <subscript>2</subscript> ](ClO <subscript>4</subscript> ) <subscript>2</subscript> ·MeNO <subscript>2</subscript> ( 2 ), and [Fe(bpCOOEt <subscript>2</subscript> p) <subscript>2</subscript> ](ClO <subscript>4</subscript> ) <subscript>2</subscript> ·2MeNO <subscript>2</subscript> ( 3 ) have been prepared and characterized. They show interesting spin-crossover (SCO) properties ranging from partial to complete thermal spin 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(bpCOOEt <subscript>2</subscript> p) <subscript>2</subscript> ](ClO <subscript>4</subscript> ) <subscript>2</subscript> ·MeNO <subscript>2</subscript> ( 2·MeNO <subscript> 2 </subscript> ), [Fe(bpCOOEt <subscript>2</subscript> p) <subscript>2</subscript> ](ClO <subscript>4</subscript> ) <subscript>2</subscript> ·MeCN ( 2·MeCN ), [Fe(bpCOOEt <subscript>2</subscript> p) <subscript>2</subscript> ](ClO <subscript>4</subscript> ) <subscript>2</subscript> ·0.5Me <subscript>2</subscript> CO (2·Me <subscript> 2 </subscript> CO ), and [Fe(bpCOOEt <subscript>2</subscript> p) <subscript>2</subscript> ](ClO <subscript>4</subscript> ) <subscript>2</subscript> ·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·Me <subscript> 2 </subscript> CO 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.<br />Competing Interests: The authors declare no competing financial interest.<br /> (© 2023 The Authors. Published by American Chemical Society.)
Details
- Language :
- English
- ISSN :
- 1528-7483
- Volume :
- 23
- Issue :
- 4
- Database :
- MEDLINE
- Journal :
- Crystal growth & design
- Publication Type :
- Academic Journal
- Accession number :
- 37038402
- Full Text :
- https://doi.org/10.1021/acs.cgd.2c01524