She Jie, Pei Wei, Zhou Si, Zhao Jijun
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
J Phys Chem Lett. 2022 Jun 30;13(25):5873-5880. doi: 10.1021/acs.jpclett.2c01522. Epub 2022 Jun 21.
Rational control of the luminescent properties of ligand-protected coinage metal clusters has long been pursued but remains challenging. Here we explore the crucial structural and electronic factors governing the fluorescence of a diphosphine-protected [Au(dppe)Cl] cluster by time-dependent density functional theory calculations. By substituting the central Au atom with group 5 to group 11 transition metal atoms, the emission wavelength is adjustable from red to blue, accompanied by enhanced fluorescence intensity compared with the undoped cluster. The evolution of light-emitting behavior upon doping and the corresponding roles of the dopant, Au cage, ligands, and their interplay are interpreted at the electronic structure level. In particular, strong dopant-Au cage interaction associated with large electron-hole overlap on the dopant are is a key factor to endow large emission energy and intensity. These theoretical results provide vital guidance for designing atomically precise nanoclusters with visible fluorescence and high quantum yield for practical uses.
长期以来，人们一直在追求对配体保护的货币金属簇发光性质的合理控制，但这仍然具有挑战性。在这里，我们通过含时密度泛函理论计算，探索了控制二膦保护的[Au(dppe)Cl]簇荧光的关键结构和电子因素。通过用第5族到第11族过渡金属原子取代中心Au原子，发射波长可从红色调节到蓝色，与未掺杂的簇相比，荧光强度增强。在电子结构水平上解释了掺杂时发光行为的演变以及掺杂剂、Au笼、配体及其相互作用的相应作用。特别是，与掺杂剂上大的电子-空穴重叠相关的强掺杂剂-Au笼相互作用是赋予大发射能量和强度的关键因素。这些理论结果为设计具有可见荧光和高量子产率的原子精确纳米簇以供实际应用提供了重要指导。
