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Conformation-dependent phosphorescence emission of individual mononuclear ruthenium-(ii)-bis-terpyridine complexes.
Physical Chemistry Chemical Physics : PCCP 2018 October 4
The potential of supramolecular transition metal coordination complexes to form robust, long-living, radiative charge transfer states makes this class of triplet state emitters ideal candidates for application as photosensitizes or in photonic devices. Antenna-enhanced phosphorescence experiments on single Ru2+-bis-terpyridine complexes incorporated into a thin PMMA film show that phosphorescence emission spectra can exhibit shifts depending on the local environment [J. F. Herrmann, P. S. Popp, A. Winter, U. S. Schubert and C. Höppener, ACS Photonics, 2016, 3, 1897-1906]. Here, we demonstrate that the environmentally altered spectral properties of individual dual-luminescent Ru2+-bis-terpyridine complexes in PMMA and acetonitrile can be reproduced by DFT-based vibrationally resolved Franck-Condon spectra, if the phosphorescent emission of different molecular conformations is taken into account. Furthermore, we demonstrate that the triplet emission of these complexes occurs from a metal-to-ligand charge transfer (MLCT) state.
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