Experimental and Computational Evidences of the Intermolecular Motifs in the Crystal Packing of Luminescent Pentacoordinated Gallium(III) Complexes

This paper reports the synthesis, characterization, photophysical and structural properties of the homologous series of good emitting pentacoordinated GaQ'L-2 complexes 1 - 3, where Q' is 2-methylquinolin-8-olate and L is a phenolate substituted in para position with respect to the oxygen donor atom. A combined approach between the experimental structural analysis (i.e. the molecular fragments involved in intermolecular p - p interactions) and the computational study (i.e. the nature of the molecular orbitals residing therein) is discussed in order to compare the charge transport aptitude of complexes 1 - 3, in relation to the facing of their LUMO/LUMO, HOMO/HOMO and HOMO/LUMO arising from the molecular packing. The different phenolate ligands significantly change the packing characteristics of 1 - 3, with indirect effects on the electron hopping kinetics responsible for conduction in amorphous thin films. The observed preference for pyridyl - pyridyl stacking proves a faster electron conduction in comparison to hole conduction in the three complexes studied.