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

We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(iii) complexes of the form of [Ir(C^N) (N^N)]PF (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...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2016-01, Vol.45 (43), p.17195-17205
Main Authors: Rota Martir, Diego, Hedley, Gordon J, Cordes, David B, Slawin, Alexandra M Z, Escudero, Daniel, Jacquemin, Denis, Kosikova, Tamara, Philp, Douglas, Dawson, Daniel M, Ashbrook, Sharon E, Samuel, Ifor D W, Zysman-Colman, Eli
Format: Article
Language:English
Subjects:
Assemblies
Chemical Sciences
Dynamical systems
Dynamics
Electronics
Mathematical analysis
Nuclear magnetic resonance
Self assembly
Zinc
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Summary:We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(iii) complexes of the form of [Ir(C^N) (N^N)]PF (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 NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature H 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.
ISSN:1477-9226
1477-9234
DOI:10.1039/c6dt02619b