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Iridium(III) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties

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dc.contributor.authorBarbante, G.J.
dc.contributor.authorDoeven, E.H.
dc.contributor.authorFrancis, P.S.
dc.contributor.authorStringer, B.D.
dc.contributor.authorHogan, C.F.
dc.contributor.authorKheradmand, P.R.
dc.contributor.authorWilson, D.J.D.
dc.contributor.authorBarnard, P.J.
dc.date.issued2015
dc.description.abstractFour cationic heteroleptic iridium(III) complexes have been prepared from methyl- or benzyl-substituted chelating imidazolylidene or benzimidazolylidene ligands using a Ag(I) transmetallation protocol. The synthesised iridium(III) complexes were characterised by elemental analysis, ᴵH and ᶦᶟC NMR spectroscopy and the molecular structures for three complexes were determined by single crystal X-ray diffraction. A combined theoretical and experimental investigation into the spectroscopic and electrochemical properties of the series was performed in order to gain understanding into the factors influencing photoluminescence and electrochemiluminescence efficiency for these complexes, with the results compared with those of similar NHC complexes of iridium and ruthenium. The N^C coordination mode in these complexes is thought to stabilise thermally accessible non-emissive states relative to the case with analogous complexes with C^C coordinated NHC ligands, resulting in low quantum yields. As a result of this and the instability of the oxidised and reduced forms of the complexes, the electrogenerated chemiluminescence intensities for the compounds are also low, despite favourable energetics. These studies provide valuable insights into the factors that must be considered when designing new NHC-based luminescent complexes.
dc.identifier.citationDalton Transactions, 2015; 44(18):8564-8576
dc.identifier.doi10.1039/c4dt03378g
dc.identifier.issn1477-9226
dc.identifier.issn1477-9234
dc.identifier.urihttps://hdl.handle.net/11541.2/122803
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.relation.fundingARC FT100100646
dc.relation.fundingARC LE120100213
dc.relation.fundingARC DP150102741
dc.rightsCopyright 2015 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. (https://creativecommons.org/licenses/by/3.0/)
dc.source.urihttp://dx.doi.org/10.1039/c4dt03378g
dc.subjectchemiluminescence
dc.subjectspectroscopic
dc.subjectligands
dc.subjectelectrochemiluminescence
dc.subjectiridium(III)
dc.titleIridium(III) N-heterocyclic carbene complexes: an experimental and theoretical study of structural, spectroscopic, electrochemical and electrogenerated chemiluminescence properties
dc.typeJournal article
pubs.publication-statusPublished
ror.mmsid9916102996801831

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