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34447553410
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While there was no evidence for phosphorescence at room temperature, it was observed at 77 K, with a lifetime of ca. 450 ms. This is in contrast to the two lifetimes we observed at 77 K for complex 4, which were fit to lifetimes of 4.5 and 23 μs
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While there was no evidence for phosphorescence at room temperature, it was observed at 77 K, with a lifetime of ca. 450 ms. This is in contrast to the two lifetimes we observed at 77 K for complex 4, which were fit to lifetimes of 4.5 and 23 μs.
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34447546611
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While representational potential energy diagrams such as Figure 4 may appear to suggest that radiative and nonradiative processes are equally affected by the displacement along the specified nuclear coordinate, this is not necessarily the case. The two processes may occur along different coordinates, and thus, there may be significant displacement along a coordinate that impacts a radiative transition, but does not affect nonradiative decay. See ref 22. We hypothesize that this is the case with our system
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While representational potential energy diagrams such as Figure 4 may appear to suggest that radiative and nonradiative processes are equally affected by the displacement along the specified nuclear coordinate, this is not necessarily the case. The two processes may occur along different coordinates, and thus, there may be significant displacement along a coordinate that impacts a radiative transition, but does not affect nonradiative decay. See ref 22. We hypothesize that this is the case with our system.
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25844461398
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Polyansky, D. E.; Danilov, E. O.; Voskresensky, S. V.; Rodgers, M. A. J.; Neckers, D. C. J. Am. Chem. Soc. 2005, 127, 13452-13453.
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Neckers, D.C.5
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0142042830
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Note that there is some disagreement in the field about the contribution of cumulenic structures to the excited state of phenylenethynylenes; see: Beeby, A, Findlay, K. S, Low, P. L, Marder, T. B, Matousek, P, Parker, A. W, Rutter, S. R, Towrie, M. Chem. Comm. 2003, 2406-2407
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Note that there is some disagreement in the field about the contribution of cumulenic structures to the excited state of phenylenethynylenes; see: Beeby, A.; Findlay, K. S.; Low, P. L.; Marder, T. B.; Matousek, P.; Parker, A. W.; Rutter, S. R.; Towrie, M. Chem. Comm. 2003, 2406-2407.
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0012569919
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Belser, P.; von Zelewsky, A.; Juris, A.; Barigelletti, F.; Balzani, V. Chem. Phys. Lett. 1984, 104, 100-104.
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Belser, P.1
von Zelewsky, A.2
Juris, A.3
Barigelletti, F.4
Balzani, V.5
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We have also considered and eliminated the possibility of aggregation; there is no evidence of concentration effects in the luminescence experiments, and no aggregation observed in the NMR, which is measured at a concentration several orders of magnitude above that used in the spectroscopy experiments. Formation of transient aggregates in the form of excimers is eliminated due to the absence of a rise time in the time-resolved experiments
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We have also considered and eliminated the possibility of aggregation; there is no evidence of concentration effects in the luminescence experiments, and no aggregation observed in the NMR, which is measured at a concentration several orders of magnitude above that used in the spectroscopy experiments. Formation of transient aggregates in the form of excimers is eliminated due to the absence of a rise time in the time-resolved experiments.
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20644435559
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Of course, in the ground state, there is a very low barrier to rotation about the -C≡C- unit; see: Miljanić, O. S, Han, S, Holmes, D, Schaller, G. R, Volhardt, K. P. C. Chem. Commun. 2005, 2606-2608 and references therein. This is not the case in the excited state
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Of course, in the ground state, there is a very low barrier to rotation about the -C≡C- unit; see: Miljanić, O. S.; Han, S.; Holmes, D.; Schaller, G. R.; Volhardt, K. P. C. Chem. Commun. 2005, 2606-2608 and references therein. This is not the case in the excited state.
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This is apparent from the excited state energies, lifetimes, and the fact that these states are populated with close to unit quantum efficiencies as judged from singlet dioxygen sensitization; B. Hernandez; M. Selke, unpublished results
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This is apparent from the excited state energies, lifetimes, and the fact that these states are populated with close to unit quantum efficiencies as judged from singlet dioxygen sensitization; B. Hernandez; M. Selke, unpublished results.
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