Unveiling Photodeactivation Pathways for a New Iridium(III) Cyclometalated Complex

We report the synthesis and characterization of a neutral heteroleptic IrIII complex bearing 6‐fluoro‐2‐phenylbenzo[d]thiazole as cyclometalating ligand and (Z)‐6‐(9H‐carbazol‐9‐yl)‐5‐hydroxy‐2,2‐dimethylhex‐4‐en‐3‐one as ancillary ligand. The photodeactivation mechanisms have been elucidated throug...

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Bibliographic Details
Published in:Chemistry : a European journal 2013-11, Vol.19 (46), p.15639-15644
Main Authors: Escudero, Daniel, Heuser, Eike, Meier, Robert J., Schäferling, Michael, Thiel, Walter, Holder, Elisabeth
Format: Article
Language:English
Subjects:
Chemistry
Deactivation
density functional calculations
Density functional theory
Excitation
iridium
Ligands
Mathematical analysis
non-adiabatic phenomena
Optical sensors
Pathways
Photochemical
photochemistry
photophysics
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Summary:We report the synthesis and characterization of a neutral heteroleptic IrIII complex bearing 6‐fluoro‐2‐phenylbenzo[d]thiazole as cyclometalating ligand and (Z)‐6‐(9H‐carbazol‐9‐yl)‐5‐hydroxy‐2,2‐dimethylhex‐4‐en‐3‐one as ancillary ligand. The photodeactivation mechanisms have been elucidated through extensive density functional theory (DFT) calculations. The active role of metal‐centered (3MC) triplet excited states in the nonradiative deactivation pathways is, for first time, confirmed in such complexes. The art of relaxing: Gaining knowledge on the photochemical processes occurring in IrIII cyclometalated complexes is the key to optimize their potential application, for example, in light‐emitting diodes or as probes for optical sensors. This work demonstrates that metal‐centered (3MC) triplet excited states are responsible for the nonradiative deactivation of a new IrIII cyclometalated complex (see figure; S0=ground state, T1=lowest triplet excited state, MECP=minimum energy crossing point).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201301291