Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems

Diego Rota Martir, Gordon J. Hedley, David B. Cordes, Alexandra M. Z. Slawin, Daniel Escudero, Denis Jacquemin, Tamara Kosikova, Douglas Philp, Daniel M. Dawson, Sharon E. Ashbrook, Ifor D. W. Samuel, Eli Zysman-Colman

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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 temperature 1H 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.
Original languageEnglish
Pages (from-to)17195-17205
Number of pages10
JournalDalton Transactions
Volume45
Issue number43
Early online date22 Sept 2016
DOIs
Publication statusPublished - 22 Nov 2016

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