Journal article
Effect of Axially Projected Oligothiophene Pendants and Nitro-Functionalized Diimine Ligands on the Lowest Excited State in Cationic Ir(III) bis-Cyclometalates
Inorganic chemistry, Vol.51(9), pp.5082-5094
05/07/2012
DOI: 10.1021/ic202573y
PMID: 22515216
Abstract
The novel terthiophene (3T) oligomer 6 and a series of cationic Ir(III) bis-cyclometalates [Ir(C∧N)2(N∧N)]PF69–12 were prepared. The synthesis, characterization, electrochemical, and photophysical properties are reported. The cyclometalating ligands (C∧N) are 2-phenylpyridinato (ppy) or the 3T oligomer (3T-ppy), asymmetrically capped in the 5 and 5″ positions with the ppy and mesityl groups. The diimine ligands (N∧N) are 2,2′-bipyridine (bpy) or 4-NO2-bipyridine (4-NO2-bpy). Hybrid metal-organic complexes 11 and 12 bear 3T-pendants ligated through the ppy cap, 10 and 12 contain NO2 functionalized diimines, whereas 9 contains neither. Structural characterization of 10 by single crystal X-ray diffraction confirms the presence of the NO2 substituent and pseudo-octahedral coordination geometry about the Ir(III) ion. Cyclic voltammetry highlights the large electron withdrawing effect of the NO2 substituent, providing an 850 mV shift toward lower potentials for the first diimine centered reduction of 10 and 12. Strong overlap of the intense π → π* absorptions of the 3T-pendants with Ir(III) charge transfer bands is evident in complexes of 11 and 12, precluding the possibility for selective excitation of either chromophore. Photoexcitation (λex = 400 nm) of the series affords strong luminescence from the 3T oligomer 6 and the unsubstituted 9, with ϕem = 0.11. In stark contrast the NO2 and 3T functionalized complexes 10–12 display near total quenching of luminescence. Computations of the ground and excited state electronic structure using density functional theory (DFT) and time-dependent DFT (TD-DFT) indicate that both the NO2 and 3T substituents play an important role in excited state deactivation of complexes 10–12. A substantial electronic contribution of the NO2 substituent results in stabilization of the diimine based molecular orbital (MO) and offers an efficient nonradiative decay pathway for the excited state. Spin–orbit coupling effects of the Ir(III) ion lead to efficient population of the low lying, nonluminescent, triplet states centered on the 3T-pendants.
Details
- Title: Subtitle
- Effect of Axially Projected Oligothiophene Pendants and Nitro-Functionalized Diimine Ligands on the Lowest Excited State in Cationic Ir(III) bis-Cyclometalates
- Creators
- Kyle R. Schwartz - University of MinnesotaRaghu Chitta - University of MinnesotaJon N. Bohnsack - University of MinnesotaDarren J. Ceckanowicz - University of MinnesotaPere Miró - University of MinnesotaChristopher J. Cramer - University of MinnesotaKent R. Mann - University of Minnesota
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.51(9), pp.5082-5094
- DOI
- 10.1021/ic202573y
- PMID
- 22515216
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Language
- English
- Date published
- 05/07/2012
- Academic Unit
- Chemistry
- Record Identifier
- 9984618505302771
Metrics
1 Record Views