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J Chem Phys. 2012 Mar 7;136(9):094905. doi: 10.1063/1.3691105.

The role of C-H and C-C stretching modes in the intrinsic non-radiative decay of triplet states in a Pt-containing conjugated phenylene ethynylene.

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Experimentalphysik II and Bayreuth Institute of Macromolecular Science, University of Bayreuth, 95440 Bayreuth, Germany.


The intrinsic non-radiative decay (internal conversion) from the triplet excited state in phosphorescent dyes can be described by a multi-phonon emission process. Since non-radiative decay of triplet excitons can be a significant process in organic light-emitting diodes, a detailed understanding of this decay mechanism is important if the overall device efficiency is to be controlled. We compare a deuterated Pt(II)-containing phenylene ethynylene with its non-deuterated counterpart in order to investigate which phonon modes control to the non-radiative decay path. We observe that deuteration does not decrease the non-radiative decay rate. A Franck-Condon analysis of the phosphorescence spectra shows that the electronic excitation is coupled strongly to the breathing mode of the phenyl ring and the C≡C carbon stretching modes, while high-energy C-H or C-D stretching modes play an insignificant role. We, therefore, associate the internal conversion process with the carbon-carbon stretching vibrations.

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