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

Diego Rota Martir , Gordon J. Hedley , David B. Cordes (1) , Alexandra M. Z. Slawin (1) , Daniel Escudero (2) , Denis Jacquemin (2, 3) , Tamara Kosikova , Douglas Philp , Daniel M. Dawson , Sharon E. Ashbrook (4) , Ifor D. W. Samuel (5) , Eli Zysman-Colman (1)

1 University of St Andrews [Scotland]
2 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
3 IUF - Institut universitaire de France
4 School of Chemistry
5 SUPA School of Physics and Astronomy [University of St Andrews]

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 (H-1 NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature H-1 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.

Domaines: Chimie

Diego Rota Martir, Gordon J. Hedley, David B. Cordes, Alexandra M. Z. Slawin, Daniel Escudero, et al.. Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems. Dalton Transactions, 2016, 45 (43), pp.17195-17205. ⟨10.1039/c6dt02619b⟩. ⟨hal-02141578⟩