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Anion Conformation and Physical Properties in BETS Salts with the Nitroprusside Anion and its Related Ruthenium Halide (X = Cl, Br) Mononitrosyl Complexes: θ‐(BETS) 4 [Fe(CN) 5 NO], (BETS) 2 [RuBr 5 NO], and (BETS) 2 [RuCl 5 NO]
Author(s) -
Sanchez MariaElena,
Doublet MarieLiesse,
Faulmann Christophe,
Malfant Isabelle,
Cassoux Patrick,
Kushch Lyudmila A.,
Yagubskii Eduard B.
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200111)2001:11<2797::aid-ejic2797>3.0.co;2-1
Subject(s) - benzonitrile , chemistry , nitrobenzene , ruthenium , crystal structure , halide , molecule , crystallography , ion , stereochemistry , inorganic chemistry , medicinal chemistry , organic chemistry , catalysis
θ‐(BETS) 4 [Fe(CN) 5 NO] ( 1 ), (BETS) 2 [RuBr 5 NO] ( 2 ), and (BETS) 2 [RuCl 5 NO] ( 3 ) [BETS = bis(ethylenedithio)tetraselenafulvalene] have been prepared by electrocrystallisation of BETS using [Fe(CN) 5 NO] 2− or [RuX 5 NO] 2− , X = Cl or Br, as supporting electrolytes and 1,1,2‐TCE/ethanol (10 vol%) for 1 , nitrobenzene/1,2‐DCE (40 vol%)/ethanol (10 vol%) for 2 , and benzonitrile/ethanol (10%) solutions for 3 as solvents. Compound 1 exhibits a metallic behaviour down to 40 K, 2 behaves as a semiconductor and 3 as an insulator. The crystal structures of 1 , 2 , and 3 were determined by X‐ray diffraction methods. BETS molecules in 1 crystallised in a θ‐type mode. By contrast, the crystal structures of 2 and 3 show a packing of BETS molecules consisting of slipped, stacked (BETS) 2 dimers. The dimerisation is much stronger in 3 than in 2 . The physical behaviours of the three phases were investigated by means of molecular and band structure calculations and are shown to be directly related to the [MX 5 NO] (M = Fe, X = CN; M = Ru, X = Cl, Br) structural conformations.