Chiral Radical‐Cation Salts of BEDT‐TTF Containing a Single Enantiomer of Tris(oxalato)aluminate(III) and ‐chromate(III). Issue 11 (6th March 2015)

• Record Type: Journal Article
• Authors: Martin, Lee; Akutsu, Hiroki; Horton, Peter N.; Hursthouse, Michael B.; Harrington, Ross W.; Clegg, William
• Is Part Of: European journal of inorganic chemistry. Issue 11(2015)
• Page Start: 1865
• Page End: 1870
• Publication Date: 2015-03-06
• Subjects: BEDT‐TTF -- Semiconductors -- Chirality -- Conductivity -- Magnetic properties; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201500092
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Radical‐cation salts of BEDT‐TTF with chiral anions provide the opportunity to combine chirality with conductivity in the same molecular material. We report here two salts, (BEDT‐TTF)3 NaAl(C2 O4 )3 · nitromethane and (BEDT‐TTF)3 (NH4 )0.83 Cr1.17 (C2 O4 )3 · nitromethane. The former crystallises in space group P 21 and the latter in P 21 21 21 . The use of nitromethane alone as the electrolyte for electrocrystallisation produces no crystals, but the addition of chiral ( R )‐(–)‐carvone yields crystals of these two new chiral radical‐cation salts of BEDT‐TTF through chiral induction from racemic tris(oxalato)aluminate(III) and tris(oxalato)chromate starting materials. The honeycomb anion layers in these salts contain a single enantiomer of tris(oxalato)metallate and creates hexagonal cavities that are smaller than those found in the superconducting β″ salts in this tris(oxalate)metallate family, which gives preference for smaller solvents to be included, such as nitromethane. The chromium salt has a non‐stoichiometric composition of the anion layer, which provides an electron doping effect to the donor layer. Abstract : The use of a chiral electrolyte has produced two new chiral radical‐cation salts of BEDT‐TTF from racemic ammonium tris(oxalato)aluminate(III) and ‐chromate. One of the salts has a non‐stoichiometric composition of 0.11 electrons per molecule doped to the band‐insulating donor layer.