Spontaneous Resolution of the Fe(C2O4)3 Anion and Inclusion of Chiral Guest Molecules in BEDT-TTF Radical-Cation Salts

Ogar, Joseph O.; Wallis, John D.; Blundell, Toby J.; Rusbridge, Elizabeth K.; Mantle, Alex; Akutsu, Hiroki; Nakazawa, Yasuhiro; Imajo, Shusaku; Martin, Lee

Abstract

We report the synthesis of three radical-cation salts of BEDT-TTF from racemic tris(oxalato)ferrate by electrocrystallization in the presence of chiral molecules. In the presence of enantiopure l-(+)-tartaric acid, we observe spontaneous resolution of the labile tris(oxalato)ferrate anion to produce the chiral radical-cation salt α-(BEDT-TTF)5[Δ-Fe(C2O4)3].[l-(+)-tartaric acid]2 which contains only the Δ enantiomer of Fe(C2O4)3. Using enantiopure (R)-(−)-3-hydroxytetrahydrofuran as an additive gives α-(BEDT-TTF)12[Fe(oxalate)3]2.(H2O)16.ethanol.(R)-(−)-3-hydroxytetrahydrofuran, which includes the chiral guest and contains a racemic mixture of Λ and Δ enantiomers of Fe(C2O4)3. Enantiopure (S)-phenyloxirane is hydrolyzed to racemic 1-phenylethane-1,2-diol to produce racemic β”-β”-(BEDT-TTF)4(H2O/H3O)Fe(C2O4)3.1-phenylethane-1,2-diol.

Citation

Ogar, J. O., Wallis, J. D., Blundell, T. J., Rusbridge, E. K., Mantle, A., Akutsu, H., Nakazawa, Y., Imajo, S., & Martin, L. (2025). Spontaneous Resolution of the Fe(C2O4)3 Anion and Inclusion of Chiral Guest Molecules in BEDT-TTF Radical-Cation Salts. Inorganic Chemistry, 64(2), 1075-1084. https://doi.org/10.1021/acs.inorgchem.4c04622

• Journal Article Type: Article
• Acceptance Date: Dec 20, 2024
• Online Publication Date: Jan 6, 2025
• Publication Date: Jan 20, 2025
• Deposit Date: Jan 8, 2025
• Publicly Available Date: Feb 14, 2025
• Journal: Inorganic Chemistry
• Print ISSN: 0020-1669
• Electronic ISSN: 1520-510X
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 64
• Issue: 2
• Pages: 1075-1084
• DOI: https://doi.org/10.1021/acs.inorgchem.4c04622
• Public URL: https://durham-repository.worktribe.com/output/3326962