School of Chemistry and Chemical Engineering, Southwest University, Key Laboratory of Luminescence and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, Chongqing, 400715, China.
Photochem Photobiol Sci. 2019 Oct 9;18(10):2421-2429. doi: 10.1039/c9pp00251k.
Carboranes feature a wealth of unique structures and properties in phosphorescent transition-metal complexes (PTMCs). Herein, we identify the influence between the electronic structure in carboranes and the main ligand based on the density functional theory (DFT) and time-dependent density functional theory (TD-DFT), which affects the phosphorescence properties of carborane-containing Pt compounds. Furthermore, the mechanism, including singlet-triplet splitting energies ΔE(Sn - T1), transition dipole moment for S0 - Sn transitions, the zero-field splitting (ZFS), the radiative decay rate constant (kr), the Huang-Rhys factor (S), and the spin-orbit coupling (SOC) matrix elements <T1|HSOC|Sn> have been carefully investigated. The results presented here reveal the functional action 1,1'-bis(o-carborane) contributes to the emission process owing to the manipulation of main ligand dtb-bpy and complex 1a shows promising prospects for achieving highly efficient phosphorescence via engineering the conjugation of the main ligand dtb-bpy.
碳硼烷在磷光过渡金属配合物（PTMCs）中具有丰富的独特结构和性质。本文基于密度泛函理论（DFT）和含时密度泛函理论（TD-DFT），确定了电子结构与主配体之间的影响，这影响了含碳硼烷的 Pt 化合物的磷光性质。此外，我们还仔细研究了包括单线态-三线态分裂能 ΔE(Sn - T1)、S0-Sn 跃迁的跃迁偶极矩、零场分裂（ZFS）、辐射衰减速率常数（kr）、黄-昌因子（S）和自旋轨道耦合（SOC）矩阵元<T1|HSOC|Sn>在内的机制。这里呈现的结果表明，1,1'-双（o-碳硼烷）的功能作用有助于发射过程，这是由于主配体 dtb-bpy 的操纵，并且通过工程化主配体 dtb-bpy 的共轭，复合物 1a 显示出实现高效磷光的广阔前景。
