Manipulating Excited State Properties of Iridium Phenylpyridine Complexes with "Push-Pull" Substituents.

Autor: Turner EE; Department of Chemistry and Chemical Biology, The University of New Mexico, Albuquerque, New Mexico 87131, United States., Breen DJ; Department of Chemistry and Chemical Biology, The University of New Mexico, Albuquerque, New Mexico 87131, United States., Kosgei G; Department of Chemistry and Chemical Biology, The University of New Mexico, Albuquerque, New Mexico 87131, United States., Crandall LA; Department of Chemistry, University of Akron, Akron, Ohio 44325-3601, United States., Curtin GM; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States., Jakubikova E; Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States., O'Donnell RM; DEVCOM Army Research Laboratory, Adelphi, Maryland 20783, United States., Ziegler CJ; Department of Chemistry, University of Akron, Akron, Ohio 44325-3601, United States., Rack JJ; Department of Chemistry and Chemical Biology, The University of New Mexico, Albuquerque, New Mexico 87131, United States.
Jazyk: angličtina
Zdroj: Inorganic chemistry [Inorg Chem] 2022 Nov 28; Vol. 61 (47), pp. 18842-18849. Date of Electronic Publication: 2022 Nov 14.
DOI: 10.1021/acs.inorgchem.2c02269
Abstrakt: We have prepared a series of complexes of the type [Ir III (ppy) 2 (L] n + complexes ( 1-4 ), where ppy is a substituted 2-phenylpyridine and L is a chelating phosphine thioether ligand. The parent complex ( 1 ) comprises an unsubstituted phenylpyridine ligand, whereas complex 2 contains a nitro substituent on the pyridine ring, complex 3 features a diphenylamine group on the phenyl ring, and 4 has both nitro and diphenylamine groups. Crystallographic, 1 H NMR, and elemental analysis data are consistent with each of the chemical formulae. DFT (density functional theory) computational results show a complicated electronic structure with contributions from Ir, ppy, and the PS ligand. Ultrafast pump-probe data show strong contributions from the phenylpyridine moieties as well as strong panchromatic excited state absorption transitions. The data show that nitro and/or diphenylamine substituents dominate the spectroscopy of this series of compounds.
Databáze: MEDLINE