Synthesis, Crystal Structure, Crystal Enginering and Theoretical Calculations of Some New Re(I)-tricarbonyl Complexes with Acenaphthequinonediimine Ligands

Tricarbonyl rhenium(I) complexes of the type fac-Re(diimine)(CO)3Cl carrying polypyridyls such as o-phenanthroline or 2,2’-bipyridine ligands have been extensively studied for many years due to their exceptionally rich photophysical and photocatalytic properties [1]. These complexes possess relatively long-lived excited states which are of metal-to-ligand charge transfer (MLCT) character; they have been incorporated into a variety of π-conjugated oligomeric or polymeric systems [2]. We introduced new diimine derivatives with strong π-acceptor moieties namely BIAN which is bis (imino) acenaphthequinone instead of polypyridyls in Re (CO)3 core to form Re(CO)3(BIAN)Cl complexes.In this study, first we synthesized new Zn complexes of acnaphthequinoneimine ligands and then the BIAN ligand was extracted from its Zn complex for synthesis of new Re (CO)3 complexes. The new Re (CO)3 complexes were investigated by UV-VIS, FT-IR and 1H-NMR spectroscopic methods. Theoretical calculations were used by GAUSSIAN09, AOMix6.88 to study the electronic structure and NBO software to pursue the new intra- and intermolecular interactions such as n→π*.