Synthesis and assembly of extended quintulene

• Published in: Nature communications Vol. 11; no. 1; p. 3976
• Main Authors: Hou, Hao, Zhao, Xin-Jing, Tang, Chun, Ju, Yang-Yang, Deng, Ze-Ying, Wang, Xin-Rong, Feng, Liu-Bin, Lin, Dong-Hai, Hou, Xu, Narita, Akimitsu, Müllen, Klaus, Tan, Yuan-Zhi
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 07.08.2020; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/301/357/341; 639/638/403; 639/638/541; Activation energy; Assembly; Bilayers; Carbon; Chromatography; Coupling (molecular); Dimerization; Dimers; Entropy; Entropy of reaction; Graphene; Humanities and Social Sciences; Interlayers; Magnetic resonance spectroscopy; Mass spectroscopy; Molecular structure; multidisciplinary; NMR; NMR spectroscopy; Nuclear magnetic resonance; Optical properties; Physical chemistry; Reaction kinetics; Science; Science (multidisciplinary); Symmetry; Synthesis
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-17691-7

Quintulene, a non-graphitic cycloarene with fivefold symmetry, has remained synthetically elusive due to its high molecular strain originating from its curved structure. Here we report the construction of extended quintulene, which was unambiguously characterized by mass and NMR spectroscopy. The extended quintulene represents a naturally curved nanocarbon based on its conical molecular geometry. It undergoes dimerization in solution via π−π stacking to form a metastable, but isolable bilayer complex. Thermodynamic and kinetic characterization reveals the dimerization process as entropy-driven and following second-order kinetics with a high activation energy. These findings provide a deeper understanding of the assembly of conical nanocarbons. Comparison of optical properties of monomer and dimer points toward a H-type interlayer coupling in the dimer. Quintulene, a quintuple non-graphitic cycloarene, is challenging to synthesize. Here, the authors synthesize and characterize the cone-shaped extended quintulene and its bilayer dimer, and disclose its dimerization as an entropy-driven, second-order reaction with a substantial activation energy.