Dual-quartet phosphorescent emission in the open-shell M₁Ag₁₃ (M = Pt, Pd) nanoclusters

Dual emission (DE) in nanoclusters (NCs) is considerably significant in the research and application of ratiometric sensing, bioimaging, and novel optoelectronic devices. Exploring the DE mechanism in open-shell NCs with doublet or quartet emissions remains challenging because synthesizing open-shell NCs is difficult due to their inherent instability. Here, we synthesize two dual-emissive M₁Ag₁₃(PFBT)₆(TPP)₇ (M = Pt, Pd; PFBT = pentafluorobenzenethiol; TPP = triphenylphosphine) NCs with a 7-electron open-shell configuration to reveal the DE mechanism. Both NCs comprise a crown-like M₁Ag₁₁ kernel with Pt or Pd in the center surrounded by five PPh₃ ligands and two Ag(SR)₃(PPh₃) motifs. The combined experimental and theoretical studies revealed the origin of DE in Pt₁Ag₁₃ and Pd₁Ag₁₃. Specifically, the high-energy visible emission and the low-energy near-infrared emission arise from two distinct quartet excited states: the core-shell charge transfer and core-based states, respectively. Moreover, PFBT ligands are found to play an important role in the existence of DE, as its low-lying π* levels result in energetically accessible core-shell transitions. This novel report on the dual-quartet phosphorescent emission in NCs with an open-shell electronic configuration advances insights into the origin of dual-emissive NCs and promotes their potential application in magnetoluminescence and novel optoelectronic devices.