Charged
Bis-Cyclometalated Iridium(III) Complexes
with Carbene-Based Ancillary Ligands
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Abstract
Charged
cyclometalated (C<sup>∧</sup>N) iridium(III) complexes
with carbene-based ancillary ligands are a promising family of deep-blue
phosphorescent compounds. Their emission properties are controlled
primarily by the main C<sup>∧</sup>N ligands, in contrast to
the classical design of charged complexes where N<sup>∧</sup>N ancillary ligands with low-energy π* orbitals, such as 2,2'-bipyridine,
are generally used for this purpose. Herein we report two series of
charged iridium complexes with various carbene-based ancillary ligands.
In the first series the C<sup>∧</sup>N ligand is 2-phenylpyridine,
whereas in the second one it is 2-(2,4-difluorophenyl)-pyridine. One
bis-carbene (:C<sup>∧</sup>C:) and four different pyridine–carbene
(N<sup>∧</sup>C:) chelators are used as bidentate ancillary
ligands in each series. Synthesis, X-ray crystal structures, and photophysical
and electrochemical properties of the two series of complexes are
described. At room temperature, the :C<sup>∧</sup>C: complexes
show much larger photoluminescence quantum yields (Φ<sub>PL</sub>) of ca. 30%, compared to the N<sup>∧</sup>C: analogues (around
1%). On the contrary, all of the investigated complexes are bright
emitters in the solid state both at room temperature (1% poly(methyl
methacrylate) matrix, Φ<sub>PL</sub> 30–60%) and at 77
K. Density functional theory calculations are used to rationalize
the differences in the photophysical behavior observed upon change
of the ancillary ligands. The N<sup>∧</sup>C:-type complexes
possess a low-lying triplet metal-centered (<sup>3</sup>MC) state
mainly deactivating the excited state through nonradiative processes;
in contrast, no such state is present for the :C<sup>∧</sup>C: analogues. This finding is supported by temperature-dependent
excited-state lifetime measurements made on representative N<sup>∧</sup>C: and :C<sup>∧</sup>C: complexes