Diorgano-Gallium and -Indium Complexes Derived from Benzoazole Ligands: Synthesis, Characterization, Photoluminescence, and Computational Studies

作者：Pal Manoj K; Kushwah Nisha; Manna Debashree; Wadawale Amey; Sudarsan V; Ghanty Tapan K; Jain Vimal K^*

来源：Organometallics, 2013, 32(1): 104-111.

DOI：10.1021/om300855x

The reactions of triorgano-gallium and -indium etherate with benzoazole ligands 2-(2'-hydroxyphenyl)benzoxazole (Hhbo) (1a), 2-(2'-hydroxyphenyl)benzothiazole (Hhbt) (1b), and 2-(2'-hydroxyphenyl)benzimidazole (Hhbi) (1c) in benzene yielded complexes of the type [R2ML](n) with n = 1 for gallium and 2 for indium (where R = Me, Et; M = Ga, In; L = hbo, hbt, and hbi) in nearly quantitative yields. These complexes have been characterized by elemental analysis, IR, UV-vis, and NMR (H-1 and C-13{H-1}) spectroscopy. Photoluminescence studies of these complexes showed that the quantum yield is always higher than that of the corresponding ligands due to reduced intermolecular interactions in complexes as compared to free ligands. The molecular structures of [Me2Ga(hbo)] (2a) and [Me2In(mu-hbt)](2) (3b) were established by X-ray crystallography. The analyses revealed that the gallium complex exists as a four-coordinated monomer, whereas the indium complex forms a dimer comprising five-coordinated indium atoms. Density functional calculations have been carried out for computing the structural and energetic parameters of the complexes, which indicate that the formation of the monomer is favorable with the Ga3+ ion, whereas the dimeric structure is preferred with the In3+ ion.

• 出版日期2013-1-14