Abstract：
The precisely modulated synthesis of programmable light-emitting materials remains a challenge. To address this challenge, we construct four tetraphenylethylene-based supramolecular architectures (SA, SB, SC, and SD), revealing that they exhibit higher electrochemiluminescence (ECL) intensities and efficiencies than the tetraphenylethylene monomer and can be classified as highly efficient and precisely modulated intramolecular aggregation-induced electrochemiluminescence (PI-AIECL) systems. The best-performing system (SD) shows a high ECL cathodic efficiency exceeding that of the benchmark tris(2,2\'-bipyridyl)ruthenium(II) chloride in aqueous solution by nearly six-fold. The electrochemical characterization of these architectures in an organic solvent provides deeper mechanistic insights, revealing that SD features the lowest electrochemical band gap. Density functional theory calculations indicate that the band gap of the guest ligand in the SD structure is the smallest and most closely matched to that of the host scaffold. Finally, the SD system is used to realize ECL-based cysteine detection (detection limit=14.4 nM) in real samples. Thus, this study not only provides a precisely modulated supramolecular strategy allowing chromophores to be controllably regulated on a molecular scale, but also inspires the programmable synthesis of high-performance aggregation-induced electrochemiluminescence emitters.
摘要：
可编程发光材料的精确调制合成仍然是一个挑战。为了应对这一挑战，我们构建了四种基于四苯基乙烯的超分子结构(SA，SB,SC,和SD），揭示它们比四苯基乙烯单体表现出更高的电化学发光（ECL）强度和效率，并且可以归类为高效和精确调制的分子内聚集诱导的电化学发光（PI-AIECL）系统。性能最佳的系统（SD）显示出高的ECL阴极效率，比水溶液中的基准三（2，2'-联吡啶）氯化钌（II）高六倍。这些结构在有机溶剂中的电化学表征提供了更深入的机理见解，揭示SD具有最低的电化学带隙。密度泛函理论计算表明，SD结构中客体配体的带隙最小，与主体支架的带隙最接近。最后,SD系统用于在实际样品中实现基于ECL的半胱氨酸检测(检测限=14.4nM)。因此，这项研究不仅提供了一种精确调制的超分子策略，允许发色团在分子尺度上可控地调节，而且还激发了高性能聚集诱导电化学发光发射器的可编程合成。
