Donor-acceptor (DA) complexes MX 3·LL·M′X 3 (M, M′ = Al, Ga; X = Cl, Br; LL = 4,4′-bipyridyl) have been theoretically investigated at the B3LYP/pVDZ level of theory. Addition of the first molecule of MX 3 to 4,4′-bipyridyl has a similar exothermicity compared to complexes with the monodentate donor pyridine. Addition of the second molecule of MX 3 is significantly (by about 15 kJ mol -1) less exothermic. Nevertheless all 2:1 complexes (including heteroacceptor) are predicted to be stable in the vapor phase up to 660, 760, 830 and 920 K for GaBr 3, GaCl 3, AlBr 3, and AlCl 3, respectively. Four homoacceptor MX 3·4,4′bpy·MX 3 complexes have been synthesized for the first time, and their existence in the vapor phase has been proven by mass spectrometry. The theoretically predicted order of the complex stability AlCl 3 > AlBr 3 > GaCl 3 > GaBr 3 correlates well with the experimental observations of M 2X 5bpy + ion abundances in the mass spectra. The results obtained show for the first time that the synthesis of the gas-phase stable heteroacceptor complexes is feasible, which opens the prospect for their future use as single-source precursors to the stoichiometry-controlled synthesis of 13-15 alloys.

Original languageEnglish
Pages (from-to)9561-9563
Number of pages3
JournalJournal of Physical Chemistry B
Volume108
Issue number28
StatePublished - 15 Jul 2004

    Scopus subject areas

  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry
  • Materials Chemistry

ID: 17373071