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 [Au₁₃(dppe)₅Cl₂]³⁺ 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.

中文翻译：

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掺杂二膦保护的金纳米团簇中具有可调颜色的增强荧光

长期以来，人们一直在追求合理控制配体保护的造币金属簇的发光特性，但仍然具有挑战性。在这里，我们探讨了控制二膦保护的 [Au ₁₃ (dppe) ₅ Cl ₂ ] ^{3+荧光的关键结构和电子因素}通过时间相关的密度泛函理论计算聚类。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后发光行为的演变以及掺杂剂、Au 笼、配体的相应作用及其相互作用。特别是，与掺杂剂上的大电子-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级精确纳米团簇用于实际应用提供了重要指导。