A Geometrically Flexible Three-Dimensional Nanocarbon

Creators: Tang, Chun; Han, Han; Zhang, Ruihua; de Moraes, Lygia S.; Qi, Yue; Wu, Guangcheng; Jones, Christopher G.; Hernandez Rodriguez, Isabel; Jiao, Yang; Liu, Wenqi; Li, Xuesong; Chen, Hongliang; Bancroft, Laura; Zhao, Xingang; Stern, Charlotte L.; Guo, Qing-Hui; Krzyaniak, Matthew D.; Wasielewski, Michael R.; Nelson, Hosea M.¹; Li, Penghao; Stoddart, J. Fraser

1. California Institute of Technology

Abstract

The development of architecturally unique molecular nanocarbons by bottom-up organic synthesis is essential for accessing functional organic materials awaiting technological developments in fields such as energy, electronics, and biomedicine. Herein, we describe the design and synthesis of a triptycene-based three-dimensional (3D) nanocarbon, GFN-1, with geometrical flexibility on account of its three peripheral π-panels being capable of interconverting between two curved conformations. An effective through-space electronic communication among the three π-panels of GFN-1 has been observed in its monocationic radical form, which exhibits an extensively delocalized spin density over the entire 3D π-system as revealed by electron paramagnetic resonance and UV–vis–NIR spectroscopies. The flexible 3D molecular architecture of GFN-1, along with its densely packed superstructures in the presence of fullerenes, is revealed by microcrystal electron diffraction and single-crystal X-ray diffraction, which establish the coexistence of both propeller and tweezer conformations in the solid state. GFN-1 exhibits strong binding affinities for fullerenes, leading to host–guest complexes that display rapid photoinduced electron transfer within a picosecond. The outcomes of this research could pave the way for the utilization of shape and electronically complementary nanocarbons in the construction of functional coassemblies.

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Acknowledgement

The authors gratefully acknowledge the financial support from The University of Hong Kong and Northwestern University. The authors appreciate the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University for providing access to equipment necessary for relevant experiments. This research utilized the IMSERC MS, NMR, and crystallography facilities at Northwestern University, which are supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the State of Illinois, the International Institute for Nanotechnology (IIN), and Northwestern University. Partial support for this research was provided through the computational resources and staff contributions at the Quest high performance computing facility at Northwestern University, jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. This work was also supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M.R.W., transient optical absorption measurements). Additionally, this research was supported as part of the Center for Molecular Quantum Transduction, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under award DE-SC0021314 (M.D.K., EPR data and analysis). Support from the Packard Foundation (H.M.N., MicroED) is also acknowledged. I.H.R. is supported by NSF Graduate Research Fellowship under grant 2139433.

Data Availability

Experimental details, including synthesis, NMR, and computational details (PDF)

Accession Codes: CCDC for GFN-1 (2333555), C₆₀·GFN-1 (2348164), and C₇₀·GFN-1 (2348167) contain the supplementary crystallographic data for this paper.

Conflict of Interest

The authors declare no competing financial interest.

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