Tris-heteroleptic Iridium Complexes Based on Cyclometalated Ligands with Different Cores

A series of tris-heteroleptic iridium complexes of the form [Ir(C<^>N-1)(C<^>N-2)(acac)] combining 2-phenyl pyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dFppy), 1-phenylpyrazole (ppz), and 1-(2,4-difluorophenyl)pyrazole (dFppz) as the CAN ligands have been synthesized and fully characterized by NMR, X-ray crystallography, UV-vis absorption and emission spectroscopy, and electrochemical methods. It is shown that "static properties" (e.g., absorption and emission spectra and redox potentials) are primarily dictated by the overall architecture of the complex, while "dynamic properties" (e.g., excited-state lifetime and radiative and nonradiative rate constants) are, in addition, sensitive to the specific positioning of the substituents. As a result, the two complexes [Ir(dFppy)(ppz)(acac)] and [Ir(ppy) (dFppz) (acac)] have the same emission maxima and redox potentials, but their radiative and nonradiative rate constants differ significantly by a factor Then acetylacetonate (acac) was replaced by picolinate (pic), and two pairs of diastereoisomers were obtained. As expected, the use of pic as the ancillary ligand results in blue-shifted emission, stabilization of the oxidation potential, and improvement of the photoluminescence quantum yield, and only minor differences in the optoelectronic properties are found between the two diastereoisomers of each pair.


Publié dans:
Inorganic Chemistry, 56, 19, 11565-11576
Année
2017
Publisher:
Washington, Amer Chemical Soc
ISSN:
0020-1669
Laboratoires:




 Notice créée le 2017-11-08, modifiée le 2018-09-13


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