北京大学郭雪峰团队报道了单分子Suzuki-Miyaura交叉偶联的可调谐干涉效应。相关研究成果发表在2023年3月14日出版的国际学术期刊《美国化学会杂志》。

在同一装置中，负载钯催化剂的平行双分子桥被集成到单独的石墨烯电极对中。基于单分子电光谱对一种钯催化途径的完整描述，该设置能够绘制不同催化剂之间的相互关系，并证明了从单分子到整体的外推过程中出现的复杂性。Suzuki–Miyaura交叉偶联揭示了两种足够接近的单独催化剂在时间尺度上的反相关行为。

进一步的实验证据表明，溶剂诱导的长程电偶极-偶极相互作用导致了两种催化剂的破坏性干涉效应。相反，两种催化剂之间基本步骤的协同耦合提供了局部加速。这种新的通过以单事件分辨率关注多个分子的反应动力学测量形式有望在单分子和系综之间架起一座桥梁。

附：英文原文

Title: Tunable Interferometric Effects between Single-Molecule Suzuki–Miyaura Cross-Couplings

Author: Yilin Guo, Chen Yang, Lei Zhang, Xuefeng Guo

Issue&Volume: March 14, 2023

Abstract: Parallel two molecular bridges loaded with a palladium catalyst were integrated into separate pairs of graphene electrodes in the same device. Based on the complete description of the one-palladium catalytic pathway by single-molecule electrical spectroscopy, this setup enables the mapping of the cross-correlation between different catalysts and demonstrates the emergent complexity in the extrapolation from single molecule to ensemble. The anticorrelation behaviors at the time scale of two individual catalysts in sufficiently close proximity were revealed in the Suzuki–Miyaura cross-coupling. Further experimental evidence demonstrates that the long-range electric dipole–dipole interaction induced by solvent leads to the destructive interferometric effect of two catalysts. In contrast, the cooperative coupling of the elementary step between two catalysts affords a local acceleration. This new form of reaction dynamics measurement via focusing on multiple molecules with single-event resolution holds great promise to build a bridge between single molecule and ensemble.

DOI: 10.1021/jacs.3c01108

Source: https://pubs.acs.org/doi/10.1021/jacs.3c01108