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 M 1 Ag 13 (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 M 1 Ag 11 kernel with Pt or Pd in the center surrounded by five PPh 3 ligands and two Ag(SR) 3 (PPh 3 ) motifs. The combined experimental and theoretical studies revealed the origin of DE in Pt 1 Ag 13 and Pd 1 Ag 13 . 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.
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