Strategic modulation of the photonic properties of conjugated organometallic Pt–Ir polymers exhibiting hybrid CT-excited states
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Polymer 6, ([trans-Pt(PBu3)2(C≡C)2]-[Ir(dFMeppy)2(N^N)](PF6))n, (([Pt]-[Ir](PF6))n; N^N = 5,5′-disubstituted-2,2′-bipyridyl; dFMeppy = 2-(2,4-difluoro-phenyl)-5-methylpyridine) is prepared along with model compounds. These complexes are investigated by absorption and emission spectroscopy and their photophysical and electrochemical properties are measured and compared with their corresponding non fluorinated complexes. Density functional theory (DFT) and time-dependent DFT computations corroborate the nature of the excited state as being a hybrid between the metal-to-ligand charge transfer (1,3MLCT) for the trans-Pt(PBu3)2(C≡CAr)2 unit, [Pt] and the metal-to-ligand/ligand-to-ligand′ charge transfer (1,3ML′CT/LL′CT) for [Ir] with L = dFMeppy. Overall, the fluorination of the phenylpyridine group expectedly does not change the nature of the excited state but desirably induces a small blue shift of the absorption and emission bands along a slight decrease in emission quantum yields and lifetimes.
Soliman , A M , Zysman-Colman , E & Harvey , P D 2014 , ' Strategic modulation of the photonic properties of conjugated organometallic Pt–Ir polymers exhibiting hybrid CT-excited states ' Macromolecular Rapid Communications , vol Early view .
Macromolecular Rapid Communications
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article: Soliman, A. M., Zysman-Colman, E. and Harvey, P. D. (2014), Strategic Modulation of the Photonic Properties of Conjugated Organometallic Pt–Ir Polymers Exhibiting Hybrid CT-Excited States. Macromolecular Rapid Communications, which has been published in final form at http://dx.doi.org/10.1002/marc.201400542
This research was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC). Date of Acceptance: 22/10/2014
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