Crystallization-Induced Enhanced Electrochemiluminescence from a New Tris(bipyridine)ruthenium(II) Derivative

Classic tris(bipyridine)ruthenium(II) complex (Ru-bpy) with high electrochemiluminescence (ECL) efficiency still suffers from a serious aggregation-caused quenching (ACQ) problem, which greatly weakens its ECL efficiency to restrict further applications in solid-state ECL imaging and light-emitting devices. Herein, the crystallization-induced enhanced ECL (CIE-ECL) of tris(bipyridine)ruthenium(II) derivatives (Ru-TPE) are reported by decorating Ru-bpy with inherent aggregation-induced emission active tetraphenylethene (TPE), which effectively eliminates the detrimental pi-pi stacking interactions and thus helps Ru-bpy surmount notorious ACQ effect in the aqueous phase. The Ru-TPE shows negligible ECL emission in solution but produces a strong ECL emission upon crystallization. Surprisingly, the ECL efficiency of Ru-TPE crystals is 20 and 3 times higher than that of its solution and Ru-bpy crystals, respectively. Experimental and structural analysis reveals that such a CIE-ECL effect originates from the restricted intramolecular rotation and ordered molecular packing. Moreover, the high-resolution ECL imaging of a single Ru-TPE crystal is successfully demonstrated. This work provides a new design strategy for achieving high efficiency in solid-state ECL imaging and devices.