Polysubstituted Ligand Framework for Color Tuning Phosphorescent Iridium(III) Complexes

Sophie A. Fitzgerald; Haleema Y. Otaif; Christopher E. Elgar; Natalia Sawicka; Peter N. Horton; Simon J. Coles; Joseph M. Beames; Simon J.A. Pope

doi:10.1021/acs.inorgchem.1c02121

Polysubstituted Ligand Framework for Color Tuning Phosphorescent Iridium(III) Complexes

Sophie A. Fitzgerald, Haleema Y. Otaif, Christopher E. Elgar, Natalia Sawicka, Peter N. Horton, Simon J. Coles, Joseph M. Beames, Simon J.A. Pope^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

A series of ligands have been synthesized based upon a polysubstituted 2-phenylquinoxaline core structure. These ligands introduce different combinations of fluorine and methyl substituents on both the phenyl and quinoxaline constituent rings. The resultant investigation of these species as cyclometalating agents for Ir(III) gave cationic complexes of the form [Ir(C^N)₂(bipy)]PF₆ (where C^N = cyclometalating ligand; bipy = 2,2′-bipyridine). X-ray crystallographic studies were conducted on four complexes and each revealed the expected distorted octahedral geometry based upon a cis-C,C and trans-N,N ligand arrangement at Ir(III). Supporting computational studies predict that each of the complexes share the same general descriptions for the frontier orbitals. TD-DFT calculations suggest MLCT contributions to the lowest energy absorption and a likely MLCT/ILCT/LLCT nature to the emitting state. Experimentally, the complexes display tunable luminescence across the yellow-orange-red part of the visible spectrum (λ_em = 579-655 nm).

Original language	English
Pages (from-to)	15467-15484
Number of pages	18
Journal	Inorganic Chemistry
Volume	60
Issue number	20
Early online date	4 Oct 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c02121
Publication status	Published - 18 Oct 2021

Bibliographical note

Funding Information:
Cardiff University (Knowledge Economy Skills Scholarships to S.A.F. and C.E.E.) and STG Aerospace are also thanked for financial support and technical input (Dr. Andrew Hallett and Dr. Sean O’Kell). We thank the staff of the EPSRC Mass Spectrometry National Service (Swansea University) and the EPSRC UK National Crystallographic Service at the University of Southampton. We thank the Chemistry Department, Jazan University, Saudi Arabia, for financial support and a scholarship to H.Y.O.

Publisher Copyright:
© 2021 American Chemical Society. All rights reserved.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Polysubstituted Ligand Framework for Color Tuning Phosphorescent Iridium(III) Complexes",

abstract = "A series of ligands have been synthesized based upon a polysubstituted 2-phenylquinoxaline core structure. These ligands introduce different combinations of fluorine and methyl substituents on both the phenyl and quinoxaline constituent rings. The resultant investigation of these species as cyclometalating agents for Ir(III) gave cationic complexes of the form [Ir(C^N)2(bipy)]PF6 (where C^N = cyclometalating ligand; bipy = 2,2′-bipyridine). X-ray crystallographic studies were conducted on four complexes and each revealed the expected distorted octahedral geometry based upon a cis-C,C and trans-N,N ligand arrangement at Ir(III). Supporting computational studies predict that each of the complexes share the same general descriptions for the frontier orbitals. TD-DFT calculations suggest MLCT contributions to the lowest energy absorption and a likely MLCT/ILCT/LLCT nature to the emitting state. Experimentally, the complexes display tunable luminescence across the yellow-orange-red part of the visible spectrum (λem = 579-655 nm).",

author = "Fitzgerald, {Sophie A.} and Otaif, {Haleema Y.} and Elgar, {Christopher E.} and Natalia Sawicka and Horton, {Peter N.} and Coles, {Simon J.} and Beames, {Joseph M.} and Pope, {Simon J.A.}",

note = "Funding Information: Cardiff University (Knowledge Economy Skills Scholarships to S.A.F. and C.E.E.) and STG Aerospace are also thanked for financial support and technical input (Dr. Andrew Hallett and Dr. Sean O{\textquoteright}Kell). We thank the staff of the EPSRC Mass Spectrometry National Service (Swansea University) and the EPSRC UK National Crystallographic Service at the University of Southampton. We thank the Chemistry Department, Jazan University, Saudi Arabia, for financial support and a scholarship to H.Y.O. Publisher Copyright: {\textcopyright} 2021 American Chemical Society. All rights reserved.",

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AU - Fitzgerald, Sophie A.

AU - Otaif, Haleema Y.

AU - Elgar, Christopher E.

AU - Sawicka, Natalia

AU - Horton, Peter N.

AU - Coles, Simon J.

AU - Beames, Joseph M.

AU - Pope, Simon J.A.

N1 - Funding Information: Cardiff University (Knowledge Economy Skills Scholarships to S.A.F. and C.E.E.) and STG Aerospace are also thanked for financial support and technical input (Dr. Andrew Hallett and Dr. Sean O’Kell). We thank the staff of the EPSRC Mass Spectrometry National Service (Swansea University) and the EPSRC UK National Crystallographic Service at the University of Southampton. We thank the Chemistry Department, Jazan University, Saudi Arabia, for financial support and a scholarship to H.Y.O. Publisher Copyright: © 2021 American Chemical Society. All rights reserved.

PY - 2021/10/18

Y1 - 2021/10/18

N2 - A series of ligands have been synthesized based upon a polysubstituted 2-phenylquinoxaline core structure. These ligands introduce different combinations of fluorine and methyl substituents on both the phenyl and quinoxaline constituent rings. The resultant investigation of these species as cyclometalating agents for Ir(III) gave cationic complexes of the form [Ir(C^N)2(bipy)]PF6 (where C^N = cyclometalating ligand; bipy = 2,2′-bipyridine). X-ray crystallographic studies were conducted on four complexes and each revealed the expected distorted octahedral geometry based upon a cis-C,C and trans-N,N ligand arrangement at Ir(III). Supporting computational studies predict that each of the complexes share the same general descriptions for the frontier orbitals. TD-DFT calculations suggest MLCT contributions to the lowest energy absorption and a likely MLCT/ILCT/LLCT nature to the emitting state. Experimentally, the complexes display tunable luminescence across the yellow-orange-red part of the visible spectrum (λem = 579-655 nm).

AB - A series of ligands have been synthesized based upon a polysubstituted 2-phenylquinoxaline core structure. These ligands introduce different combinations of fluorine and methyl substituents on both the phenyl and quinoxaline constituent rings. The resultant investigation of these species as cyclometalating agents for Ir(III) gave cationic complexes of the form [Ir(C^N)2(bipy)]PF6 (where C^N = cyclometalating ligand; bipy = 2,2′-bipyridine). X-ray crystallographic studies were conducted on four complexes and each revealed the expected distorted octahedral geometry based upon a cis-C,C and trans-N,N ligand arrangement at Ir(III). Supporting computational studies predict that each of the complexes share the same general descriptions for the frontier orbitals. TD-DFT calculations suggest MLCT contributions to the lowest energy absorption and a likely MLCT/ILCT/LLCT nature to the emitting state. Experimentally, the complexes display tunable luminescence across the yellow-orange-red part of the visible spectrum (λem = 579-655 nm).

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

Polysubstituted Ligand Framework for Color Tuning Phosphorescent Iridium(III) Complexes

Abstract

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