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The results demonstrate the different roles of switchable intramolecular π···π interactions and the geometrical configuration of the Cu(μ-dppm)2Cu unit in this stimuli-responsive luminescence and potential applications of such stimuli-responsive luminescence in optical sensing and anticounterfeiting encryption technologies and deepen the understanding of such stimuli-responsive luminescence originating from switchable intramolecular π···π interactions. In addition, it is clearly suggested that the rational utilization of switchable intr