Two mixed ligand zinc(II) complexes containing 1,2-benzenedithiol (bdt) and having the formula Zn(bdt)(N-N) where N-N are the asymmetrically substituted diimine ligands 2,3,4,7,8-pentamethyl-1,10-phenanthroline (pmp, complex I) or 2,3,4,7,8-pentamethyl-9-isopropyl-1,10-phenanthroline (ippmp, complex II) have been synthesized. The crystal structures of both compounds have been determined by X-ray crystallography and indicate mononuclear complexes with a distorted tetrahedral geometry around the zinc atom. In complex II an unusual structural feature appears showing a bulky substituent group bending towards a more sterically hindered site. The packing diagram shows that this occurs due to intramolecular interactions between the bulkier substituent and a phenanthroline ligand on a neighboring molecule in the unit cell. Both complexes are weakly emissive in the solid state at room temperature and exhibit multiple emissions at lower temperatures in a polymethylmethacrylate (PMMA) film. The observed multiple emissions are believed to be metal assisted ligand to ligand charge transfer (LLCT) bands overlaying unresolved intraligand ππ* transitions.

Synthesis, structural characterization and luminescent behavior of heteroleptic zinc(II) complexes employing novel asymmetric N,N-heterocyclic ligands

251st National Meeting (2016)

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