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Theoretical Insights into the Photo-Deactivation of Emitting Triplet Excited State of (C^N)Pt(O^O) Complexes: Radiative and Nonradiative Decay Processes

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journal contribution
posted on 12.08.2016, 00:00 by Yanyan Xu, Yafei Luo, Ming Li, Rongxing He, Wei Shen
In this study, density functional theory (DFT) and time-dependent DFT were employed to elucidate the photo-deactivation mechanisms of (C^N)­Pt­(O^O) complexes 14 (where C^N = 2-phenylpyridine derivatives, O^O = dipivolylmethanoate). To make thorough understanding of the radiative decay, the singlet–triplet splitting energies ΔE(Sn–T1) (n = 1, 2, 3, 4, ...), transition dipole moment μ­(Sn) for S0–Sn transitions and the spin–orbit coupling (SOC) matrix elements ⟨T1|HSOC|Sn⟩ were all calculated. Moreover, the spin–orbit coupling between T1 and S0 ⟨T1|HSOC|S0⟩ and Huang–Rhys factors were calculated to estimate the temperature-independent nonradiative decay processes. Meanwhile, the thermal deactivation via metal-centered 3MC was described to analyze the temperature-dependent nonradiative decay processes. As a result, the effective SOC interaction between the lowest triplet and singlet excited states successfully rationalize why complexes 1 and 3 have higher radiative decay rate constant than that of complex 2, while the larger ⟨T1|HSOC|S0⟩ and lower energy barrier for thermal deactivation in 3 reasonably explains why 3 has larger nonradiative rate than that of 1 and 2. Consequently, it can be concluded that it is the ⟨T1|HSOC|S0⟩ and thermal population of 3MC that account for the nonemissive behavior of (C^N)­Pt­(O^O) complexes, and controlling π-conjugation is an efficient method for tuning phosphorescence properties of transition-metal complexes.