Enhanced π–π Stacking between Dipole-Bearing Single Molecules Revealed by Conductance Measurement

Zhang, Chengyang and Cheng, Jie and Wu, Qingqing and Hou, Songjun and Feng, Sai and Jiang, Bo and Lambert, Colin J. and Gao, Xike and Li, Yueqi and Li, Jinghong (2023) Enhanced π–π Stacking between Dipole-Bearing Single Molecules Revealed by Conductance Measurement. Journal of the American Chemical Society, 145 (3). pp. 1617-1630. ISSN 0002-7863

Text (Enhanced π-π stacking between dipole-bearing single molecules revealed by conductance measurement)
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Abstract

Dipoles are widely involved in π-π interactions and are central to many chemical and biological functions, but their influence on the strength of π-π interactions remains unclear. Here, we report a study of π-π interaction between azulene-based, polar single molecules and between naphthalene-based, nonpolar single molecules. By performing scanning tunneling microscopy break junction measurements of single-molecule conductance, we show that the π-stacked dimers formed by the azulene-based, polar aromatic structures feature higher electrical conductivity and mechanical stability than those formed by the naphthalene-based, nonpolar molecules. Mechanical control of π-π interactions in both rotational and translational motion reveals a sensitive dependence of the stacking strength on relative alignment between the dipoles. The antiparallel alignment of the dipoles was found to be the optimal stacking configuration that underpins the observed enhancement of π-π stacking between azulene-based single molecules. Density functional theory calculations further explained the observed enhancement of stacking strength and the corresponding charge transport efficiency. Our experimental and theoretical results show that the antiparallel alignment of the dipole moments significantly enhances the electronic coupling and mechanical stability of π-π stacking. In addition, in the formation of single-molecule junctions, the azulene group was experimentally and theoretically proved to form a Au−π contact with electrodes with high charge transport efficiency. This paper provides evidence and interpretation of the role of dipoles in π-π interactions at the single-molecule level and offers new insights into potential applications in supramolecular devices.