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The Effect of Aryl Substitution on the Properties of a Series of Highly Absorptive Cationic Iridium(III) Complexes Bearing Ancillary Bis(arylimino)acenaphthene Ligands
Author(s) -
Hasan Kamrul,
ZysmanColman Eli
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300583
Subject(s) - chemistry , iridium , acenaphthene , ligand (biochemistry) , cationic polymerization , aryl , absorption spectroscopy , cyclic voltammetry , photochemistry , substituent , absorption (acoustics) , medicinal chemistry , electrochemistry , alkyl , polymer chemistry , organic chemistry , biochemistry , receptor , physics , electrode , quantum mechanics , acoustics , anthracene , catalysis
A family of cationic heteroleptic iridium(III) complexes of the form [Ir(ppy) 2 (Ar‐BIAN)]PF 6 (ppyH = 2‐phenylpyridine) in which Ar‐BIAN [bis(arylimino)acenaphthene] acts as an ancillary ligand were synthesized and characterized. Their ground‐state electronic structures were probed by UV/Vis spectroscopy and cyclic voltammetry. The X‐ray structure of [Ir(ppy) 2 (4‐MeO 2 CPh‐BIAN)]PF 6 was solved. The first and second reduction wave potentials are strongly influenced by the substituent on the Ar‐BIAN ligand and follow a Hammett relationship. The absorption spectra for complexes incorporating an electron‐donating Ar‐BIAN ligand are noticeably redshifted, and absorption tails off past 800 nm. Notably, the absorption spectrum for [Ir(ppy) 2 (4‐NMe 2 Ph‐BIAN)]PF 6 shows an intense band centered at 576 nm, and it was assigned computationally to a mixed metal‐to‐ligand charge‐transfer/ligand‐to‐ligand charge‐transfer state.