期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 48, 页码 22026-22034出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c09204
关键词
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资金
- Center for Nanothread Chemistry, a National Science Foundation (NSF) Center for Chemical Innovation [CHE-1832471]
- Alfred P. Sloan Foundation [FG-2021-15490]
- Pennsylvania State University Eberly College of Science (ECoS) Postdoctoral Scholar Program
- National Science Foundation CAREER award [NSF-CHE-2144556]
- Massachusetts Life Science Center grant [G00006360]
- DOE-NNSA's Office of Experimental Sciences
- DOE Office of Science by Argonne National Laboratory [DE-AC02-06CH11357]
This study presents a novel approach to synthesize nanotubes at lower pressures using photochemical methods. The photochemically mediated polymerization of pyridine and furan aromatic precursors allows for the formation of nanotubes at reduced pressures. The maximum pressure required for furan-derived nanotubes is reduced by 1.9-fold, and the pressure required for pyridine-derived nanotubes is reduced by 1.4-fold.
Nanothreads are emerging one-dimensional sp3- hybridized materials with high predicted tensile strength and a tunable band gap. They can be synthesized by compressing aromatic or nonaromatic small molecules to pressures ranging from 15-30 GPa. Recently, new avenues are being sought that reduce the pressure required to afford nanothreads; the focus has been placed on the polymerization of molecules with reduced aromaticity, favorable stacking, and/or the use of higher reaction temperatures. Herein, we report the photochemically mediated polymerization of pyridine and furan aromatic precursors, which achieves nanothread formation at reduced pressures. In the case of pyridine, it was found that a combination of slow compression/ decompression with broadband UV light exposure yielded a crystalline product featuring a six-fold diffraction pattern with similar interplanar spacings to previously synthesized pyridine-derived nanothreads at a reduced pressure. When furan is compressed to 8 GPa and exposed to broadband UV light, a crystalline solid is recovered that similarly demonstrates X-ray diffraction with an interplanar spacing akin to that of the high-pressure synthesized furan-derived nanothreads. Our method realizes a 1.9-fold reduction in the maximum pressure required to afford furan-derived nanothreads and a 1.4-fold reduction in pressure required for pyridine derived nanothreads. Density functional theory and multiconfigurational wavefunction-based computations were used to understand the photochemical activation of furan and subsequent cascade thermal cycloadditions. The reduction of the onset pressure is caused by an initial [4+4] cycloaddition followed by increasingly facile thermal [4+2]-cycloadditions during polymerization.
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