The University of Southampton
University of Southampton Institutional Repository

A polysubstituted ligand framework for color tuning phosphorescent iridium(III) complexes

A polysubstituted ligand framework for color tuning phosphorescent iridium(III) complexes
A polysubstituted ligand framework for color tuning phosphorescent iridium(III) complexes
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).
0020-1669
15467–15484
Fitzgerald, Sophie A.
2c97e1e5-2148-47b1-8bfe-7cb0c8f2136b
Otaif, Haleema Y.
1b365536-1683-40d5-b6d2-3f869cdac579
Elgar, Christopher E.
f59426b7-72ba-4125-96e3-b9b63da790ff
Sawicka, Natalia
a3e59f0d-fca7-4ca4-a418-9034cfe6cfa5
Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Beames, Joseph M.
73b04545-4859-44ad-999e-551f82924c29
Pope, Simon J.A.
db9a489c-29ba-41cd-a96a-623bace0889d
Fitzgerald, Sophie A.
2c97e1e5-2148-47b1-8bfe-7cb0c8f2136b
Otaif, Haleema Y.
1b365536-1683-40d5-b6d2-3f869cdac579
Elgar, Christopher E.
f59426b7-72ba-4125-96e3-b9b63da790ff
Sawicka, Natalia
a3e59f0d-fca7-4ca4-a418-9034cfe6cfa5
Horton, Peter
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Beames, Joseph M.
73b04545-4859-44ad-999e-551f82924c29
Pope, Simon J.A.
db9a489c-29ba-41cd-a96a-623bace0889d

Fitzgerald, Sophie A., Otaif, Haleema Y., Elgar, Christopher E., Sawicka, Natalia, Horton, Peter, Coles, Simon J., Beames, Joseph M. and Pope, Simon J.A. (2021) A polysubstituted ligand framework for color tuning phosphorescent iridium(III) complexes. Inorganic Chemistry, 60 (20), 15467–15484. (doi:10.1021/acs.inorgchem.1c02121).

Record type: Article

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).

Text
Pope IC rev3 - Accepted Manuscript
Download (1MB)

More information

Accepted/In Press date: 4 October 2021
Published date: 4 October 2021
Additional 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.

Identifiers

Local EPrints ID: 454681
URI: http://eprints.soton.ac.uk/id/eprint/454681
ISSN: 0020-1669
PURE UUID: b0d47218-cef6-430a-b0b3-9a831b420e18
ORCID for Peter Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 21 Feb 2022 17:33
Last modified: 17 Mar 2024 07:06

Export record

Altmetrics

Contributors

Author: Sophie A. Fitzgerald
Author: Haleema Y. Otaif
Author: Christopher E. Elgar
Author: Natalia Sawicka
Author: Peter Horton ORCID iD
Author: Simon J. Coles ORCID iD
Author: Joseph M. Beames
Author: Simon J.A. Pope

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×