ESTIMATION OF THE ENERGIES OF INTERMOLECULAR INTERACTIONS X...Y (X=BEDT-TTF, TMTSF; Y = C60, C70) IN THE NEW MOLECULAR COMPLEXES OF FULLERENES

S.V.Konovalikhin and L.O.Atovmyan.

Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, Chernogolovka, Moscow Region, 142432, Russia.
E-mai1
knh@icp.ac.ru

An X-ray study of (BEDT-TTF)2C60 (1) (BEDT-TTF - bis(ethylenedithio)- tetrathiafulvalene) [1], (TMTSF)C602(CS2) (2) (TMTSF - tetralnethyltetraselena-fulvalene) [2] and (TMTSF)2(C60)2(C6H6) (3) [3] crystals has been made It has been established that the conformations of the BEDT-TTF and TMTSF molecules in crystals 1 - 3 are not energetically preferable. It is "boat" conformation. For example: the TMTSF molecules is folded along Se...Se line on 22 - 27o. Usually, the BEDT-TTF and TMTSF molecules has a plane ore near to plane conformation. It has been established that analogous conformation have of TMTSF molecule in the (TMTSF)X(C70)y(C6H6)z (4) crystal [4]. It has been shown that it is caused by is intermolecular interactions X...Y (X= BEDT-TTF, TMTSF; Y = C60, C70). We assume that the energy of these intermolecular interactions (W) can be estimated as it follows from the equation W = Wc- W0, where W0 is the energy of the more energetically preferable conformer of the X molecule, Wc is the energy of the X molecule conformer in crystals 1 - 4. The energies of the conformers of the BEDT-TTF and TMTSF molecules have been calculated by the SCF MO method in the 3-21G/6-31G* basis. It has been established, that the energy of the BEDT-TTF...C60 intermolecular interactions in the (BEDT-TTF)2C60 crystal is 13 kcal/mol. The energy of the TMTSF...C60 intermolecular interactions in the (TMTSF)C60 2(CS2) and (TMTSF)2(C60)2(C6H6) crystals are 3.2 - 3.4 kcal/mol. The energy of the TMTSF...C70 intermolecular interactions in the (TMTSF)X(C70)y(C6H6)z crystal are 3.0 - 3.5 kcal/mol.

  1. S.V.Konovalikhin et al. Zh. Fizich. Khimi., 1997, V. 71, 2192.
  2. S.V.Konovalikhin et al, Russ. Cheln. Bull., 1997, V.46, 1415.
  3. O.A.Dyachenko and S.V.Konovalikhin, Coordin. Khim., 1998, 000.
  4. S.V.Konovalikhin at al. unpublished results.