title: Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems.
abstract: We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(iii) complexes of the form of [Ir(C^N)2(N^N)]PF6(where C^N is mesppy = 2-phenyl-4-mesitylpyridinato and dFmesppy = 2-(4,6-difluorophenyl)-4-mesitylpyridinato and N^N is 4,4':2',2'':4'',4'''-quaterpyridine, qpy) and zinc tetraphenylporphyrin (ZnTPP), assembled through non-covalent interactions between the distal pyridine moieties of the qpy ligand located on the iridium complex and the zinc of the ZnTPP. The assemblies have been comprehensively characterized by a series of analytical techniques (1H NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature1H NMR spectroscopy) and the crystal structures have been elucidated by X-ray diffraction. The optoelectronic properties of the assemblies and the electronic interaction between the iridium and porphyrin chromophoric units have been explored with detailed photophysical measurements, supported by time-dependent density functional theory (TD-DFT) calculations.
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK. eli.zysman-colman@st-andrews.ac.uk.
authors.forename: Diego
authors.initials: D
authors.lastname: Rota Martir
authors.affiliation: Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, St Andrews, Fife, KY16 9SS, UK.
authors.forename: Gordon J
authors.initials: GJ
authors.lastname: Hedley
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK. eli.zysman-colman@st-andrews.ac.uk.
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, UK. eli.zysman-colman@st-andrews.ac.uk.
authors.forename: Alexandra M Z
authors.initials: AM
authors.lastname: Slawin
authors.affiliation: CEISAM UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
authors.forename: Daniel
authors.initials: D
authors.lastname: Escudero
authors.affiliation: CEISAM UMR CNRS 6230, Université de Nantes, 2 rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France and Institut Universitaire de France, 1, rue Descartes, 75231 Paris Cedex 5, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK. eli.zysman-colman@st-andrews.ac.uk.
authors.forename: Tamara
authors.initials: T
authors.lastname: Kosikova
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK. eli.zysman-colman@st-andrews.ac.uk.
authors.forename: Douglas
authors.initials: D
authors.lastname: Philp
authors.affiliation: EaStCHEM School of Chemistry and the Centre for Magnetic Resonance, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK.
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Dawson
authors.affiliation: EaStCHEM School of Chemistry and the Centre for Magnetic Resonance, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK.
authors.forename: Sharon E
authors.initials: SE
authors.lastname: Ashbrook
authors.affiliation: Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, St Andrews, Fife, KY16 9SS, UK.
authors.forename: Ifor D W
authors.initials: ID
authors.lastname: Samuel
authors.affiliation: Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK. eli.zysman-colman@st-andrews.ac.uk.
authors.forename: Eli
authors.initials: E
authors.lastname: Zysman-Colman