Cuprophilicity is the attractive interaction between closed shell d10 copper(I) ions. These metal-metal interactions can be strong enough to modulate the physical arrangement of atoms and affect the luminescent properties. The simple bimetallic system, [Cu2(dppm)2(MeCN)4](PF6)2 (1), has been reinvestigated. Subtle application of external stimuli (i.e. grinding, vacuum, and heat) induces dramatic changes in the luminescence. Grinding samples of non-luminescent 1 immediately produces a bright blue luminescent material identified as [Cu2(dppm)2(MeCN)2](PF6)2 (2). The crystal structure of 2 shows two 3-coordinate Cu(I) centers in a face-to-face arrangement with a short Cu-Cu separation of 2.95Å. Heating a single crystal of 1 also produces a partially desolvated material identical to 2. Recrystallization of 1 or 2 from dichloromethane produces a solvent free species, [Cu2(dppm)2](PO2F2)(PF6) (3) where adventitious water hydrolyzes one hexafluorophosphate ion upon crystallization. The synthesis, structure, and luminescence of compounds 1, 2, and 3 are reported.

Stimuli induced, “on-off” ligation in a simple [Cu2(dppm)2(solvent)n]2+ system

251st National Meeting (2016)

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