title: An Unprecedented Family of Luminescent Iridium(III) Complexes Bearing a Six-Membered Chelated Tridentate C^N^C Ligand.
abstract: A new family consisting of three luminescent neutral Ir(III) complexes with the unprecedented [Ir(C^N^C)(N^N)Cl] architecture, where C^N^C is a bis(six-membered) chelating tridentate tripod ligand derived from 2-benzhydrylpyridine (bnpy) and N^N is 4,4'-di-tert-butyl-2,2'-bipyridine (dtBubpy), is reported. X-ray crystallography reveals an unexpected and unusual double C-H bond activation of the two distal nonconjugated phenyl rings of the bnpy coupled with a very short Ir-Cl bond trans to the pyridine of the bnpy ligand. Depending on the substitution on the bnpy ligand, phosphorescence, ranging from yellow to red, is observed in dichloromethane solution. A combined study using density functional theory (DFT) and time-dependent DFT (TD-DFT) corroborates the mixed charge-transfer nature of the related excited states.
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 , Campus de Beaulieu, 35042 Rennes Cedex, France.|Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St. Andrews , St. Andrews, Fife, KY16 9ST, United Kingdom.
authors.forename: Claus
authors.initials: C
authors.lastname: Hierlinger
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 , Campus de Beaulieu, 35042 Rennes Cedex, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Roisnel
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St. Andrews , St. Andrews, Fife, KY16 9ST, United Kingdom.
authors.forename: David B
authors.identifier: http://orcid.org/0000-0002-5366-9168
authors.initials: DB
authors.lastname: Cordes
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St. Andrews , St. Andrews, Fife, KY16 9ST, United Kingdom.
authors.forename: Alexandra M Z
authors.initials: AMZ
authors.lastname: Slawin
authors.affiliation: UMR CNRS 6230, Université de Nantes, CEISAM , 2 rue de la Houssinière, 44322 Nantes Cedex 3, France.|Institut Universitaire de France , 1, Rue Descartes, 75005 Paris Cedex 5, France.
authors.forename: Denis
authors.identifier: http://orcid.org/0000-0002-4217-0708
authors.initials: D
authors.lastname: Jacquemin
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 , Campus de Beaulieu, 35042 Rennes Cedex, France.
authors.forename: Véronique
authors.initials: V
authors.lastname: Guerchais
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St. Andrews , St. Andrews, Fife, KY16 9ST, United Kingdom.
authors.forename: Eli
authors.identifier: http://orcid.org/0000-0001-7183-6022
authors.initials: E
authors.lastname: Zysman-Colman