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

Rota Martir, D. et al. (2016) Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems. Dalton Transactions, 45(43), pp. 17195-17205. (doi: 10.1039/C6DT02619B) (PMID:27722693)

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.

• Item Type: Articles
• Additional Information: EZ-C acknowledges the University of St Andrews for financial support. We thank Umicore AG for the gift of materials. IDWS acknowledges support from EPSRC (EP/J009016) and the European Research Council (grant 321305). IDWS also acknowledges support from a Royal Society Wolfson research merit award. We thank the EPSRC UK National Mass Spectrometry Facility at Swansea University for analytical services. DJ acknowledges the European Research Council (grant: 278845) and the RFI Lumomat for financial support. This research used resources of (1) the GENCICINES/IDRIS, (2) Centre de Calcul Intensif des Pays de Loire (CCIPL), and (3) a local Troy cluster.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Hedley, Dr Gordon
• Authors: Rota Martir, D., Hedley, G. J., Cordes, D. B., Slawin, A. M.Z., Escudero, D., Jacquemin, D., Kosikova, T., Philp, D., Dawson, D. M., Ashbrook, S. E., Samuel, I. D.W., and Zysman-Colman, E.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Dalton Transactions
• Publisher: Royal Society of Chemistry
• ISSN: 1477-9226
• ISSN (Online): 1477-9234