Controlling the solid-state luminescence of gold(I) N-heterocyclic carbene complexes through changes in the structure of molecular aggregates
Thermally stable, solid-state luminescent organic materials are highly desired for the development of practical applications. Herein we synthesized new gold(I) complexes with N-heterocyclic carbene ligands, which have the ability to form strong metal-organic bond. Consequently, their thermochemical stability is enhanced at temperatures around 300 °C. Precise design of the molecular structure of the ligands, with a focus on ensuring low steric hindrance around Au atoms in order to limit disturbances to Au/Au interactions, provided a complex with a densely packed crystal with a shorter intermolecular Au–Au distance (3.17 Å) than the typical distance. In the solid state, this complex exhibited strong aurophilic interactions, which generated intense phosphorescence even in air at room temperature (quantum yield=16%) in spite of absence of any phosphorescence in solution. This behavior is characteristic for solid-state luminescence referred to as aggregation-controlled emission. Furthermore, the gold (I) complex displays capacity for mechano- and vapo-chromism—that is, the ability to change color reversibly in response to the application of external stimuli. We believe that the proposed design framework, which involves controlling thermal stability and luminescence property separately, provides a new opportunity for the development of practical applications using solid-state luminescent organic molecules.
KeywordsAu complex N-heterocyclic carbene phosphorescence mechanochromism aggregation-induced emission
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This work was supported by the JSPS KAKENSHI (18K05265), JST Matching Planner Program (VP29117941122), JICA Collaboration Kick-starter Program (RU and IITH), and the Cooperative Research Program of the Network Joint Research Center for Materials and Devices (Tokyo Institute of Technology).
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