| 苯胺基团对一类Pt(Ⅱ)磷光发光材料非辐射跃迁调控的理论研究 |
| Theoretical Study on Regulation of Aniline Moiety on Non-radiative Transition of a Kind of Pt(Ⅱ) Phosphorescent Materials |
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| 摘要: 采用密度泛函（DFT）和含时-密度泛函（TD-DFT）方法研究二苯胺基团对一类Pt （Ⅱ）配合物（M1~M3）光学性质的调控。通过与实验合成的分子对比，揭示苯胺基团取代位置和数量对电子结构和光学性质的调控规律。引入苯胺基团可有效地增大金属和配体的π共轭性。逐渐增多苯胺基团导致M3分子可以有效地增大吸收光谱的强度和金属到配体的电荷转移（MLCT）占比，有利于金属对光的吸收和自旋轨道耦合。M1~M3的发射峰在602~630 nm，发射光谱归属为3MLCT和配体之间的电荷转移（3LLCT）。通过对非辐射跃迁过程，即T1（3MLCT）→ TS →金属中心三重态3MC （d-d）的研究，发现当二苯胺取代基团引入位置可以有效地增大分子内空间位阻时，形成S0和T1的系间交叉MECP能量变得更高，从而抑制了非辐射的概率，有利于发光性能提高。 |
| 关键词: 密度泛函理论 激发态 非辐射跃迁过程 金属中心三重态 |
| 基金项目: 中央高校基金（No.2017XKQY065）资助。 |
| Abstract: A series of efficient red platinum based emitter with functionalized diphenylamine moiety (M1~M3) were designed and investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT). The effect of different substituent positions on the electronic structures and optical properties were fully explored by compared with the synthesized complex. The introduction of diphenylamine moiety could effectively strengthen the π-conjugation interaction between the metal and ligand. By gradually increasing the amount of diphenylamine moiety, the intensities and the participation of metal-to-ligand charge-transfer (MLCT) for the absorption bands of M3 were enhanced, which are beneficial to collect light energy participation of metals and increase the spin-orbital coupling effect. M1~M3 exhibited red emission with the peak wavelengths at 602~630 nm. These emission spectra are mixtures of 3MLCT and ligand to ligand charge transfer (3LLCT) character. The possible non radiative process T1 (3MLCT) → TS → triplet metal-centered 3MC (d-d) state were deeply investigated, and the results show that the possibility of the non-radiative process will decrease because the surface crossing at a minimum energy crossing point (MECP) between T1 and S0 state is difficult to populate when the functionalized diphenylamine moiety is useful to enhance steric hindrance. |
| Keywords: density functional theory excited state non-radiative process metal-centered triplet state |
| 投稿时间：2020-10-23 修订日期：2020-10-23 |
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| 康国俊,李珂,任雪峰,唐洪渠.苯胺基团对一类Pt(Ⅱ)磷光发光材料非辐射跃迁调控的理论研究[J].无机化学学报,2021,37(3):569-576. |
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