Push-pull effect on the geometrical, optical and charge transfer properties of disubstituted derivatives of mer-tris(4-hydroxy-1,5-naphthyridinato) aluminum (mer-AlND3)

Abstract

AbstractTo design innovative and novel optical materials with high mobility, two kinds of disubstituted derivatives for mer-tris(4-hydroxy-1,5-naphthyridinato) aluminum (mer-AlND3) with push (EDG)–pull (EWG) substituents have been designed. The structures of mer-tris(8-EDG-2-EWG-4-hydroxy-1,5-naphthyridinato) aluminum (type I) and mer-tris(8-EWG-2-EDG-4-hydroxy-1,5-naphthyridinato) aluminum (type II) in the ground and first excited states have been optimized at the B3LYP/6-31G(D) and CIS/6-31G(D) level of theory, respectively. It can be seen from frontier molecular orbitals analysis, in all these complexes, the highest occupied molecular orbital (HOMO) is localized on the pyridine-4-ol ring of A-ligand while lowest unoccupied molecular orbital (LUMO) is on the pyridyl ring of B-ligand in ground state irrespective of electron donor/acceptor substitution present on the ligands similar to that of mer-tris(8-hydroxyquinoline) aluminum (mer-Alq3) and parent mer-AlND3.The absorption and emission wavelengths have been evaluated at the TD-PBE0/6-31G(D) level and it can be see that all the type I derivatives show blue shift while most of the type II derivatives show red shift compared to mer-AlND3. All the disubstituted complexes have showed hypsochromic shifts in both the absorption and emission spectra when compared with the calculated absorption and emission spectra respectively of mer-Alq3. It can be seen that the reorganization energies of some of the disubstituted derivatives are comparable with mer-Alq3 and these derivatives might be good candidates for emitting materials in OLED.