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

• Published in: Nature communications 2024-07, Vol.15 (1), p.5962-10, Article 5962
• Main Authors: Fang, Cao, Xu, Chang, Zhang, Wei, Zhou, Meng, Tan, Dong, Qian, Lixia, Hu, Daqiao, Jin, Shan, Zhu, Manzhou
• Format: Article
• Language: English
• Subjects: 119/118; 140/125; 639/301/357/551; 639/638/263; 639/638/439; 639/925/357/551; Charge transfer; Configurations; Emissions; Energy charge; Humanities and Social Sciences; Ligands; Medical imaging; multidisciplinary; Nanoclusters; Near infrared radiation; Optoelectronic devices; Palladium; Phosphorescence; Platinum; Science; Science (multidisciplinary); Shell stability; Synthesis
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-50289-x

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. Exploring the dual-emission mechanism in open-shell nanoclusters with doublet or quartet emissions remains challenging. Here, the authors reveal the origin of dual-quartet phosphorescent emission in the open-shell M1Ag13 (M = Pt, Pd) nanoclusters.