Crystallization-Induced Enhanced Electrochemiluminescence from Tetraphenyl Alkene Nanocrystals for Ultrasensitive Sensing.

Organic materials with diverse structures and brilliant glowing colors have been attracting extensive attention in optical electronic devices and electrochemiluminescence (ECL) fields and are currently faced with the issue of low ECL efficiency. Herein, a series of tetraphenyl alkene nanocrystals (TPA NCs) with an ordered molecular structure were synthesized to explore regularities in the crystallization-induced enhanced (CIE) ECL emission effects by altering the number and position of vinyl on the backbone of TPA molecules. Among those TPA NCs, tetraphenyl-1,3-butadiene (TPB) NCs exhibit the brightest ECL emission via a coreactant pathway, with the relative ECL efficiency of up to 31.53% versus the standard [Ru(bpy)3]2+/TEA system, which is thousands of times higher than that of free TPB molecules. The high ECL efficiency of TPB NCs originates from the effective electron transfer of unique J-aggregates on the a axis of the nanocrystals to notably promote radiative transition and the restriction on the free rotation of TPB molecules to further suppress the nonradiative transition, which has exhibited great potential in ultrasensitive biosensing, efficient light-emitting devices, and clear ECL imaging fields. As a proof of concept, since dopamine (DA) can form benzoquinone species by electrochemical oxidation to realize intermediate radical quenching and excited-state quenching on the TPB NCs/TEA system, the TPB NCs with the CIE ECL effect are used to construct an ultrasensitive ECL-sensing platform for the determination of DA with a lower detection limit of 3.1 nM.