TY - JOUR
T1 - Solid-State Pathway Control via Reaction-Directing Heteroatoms
T2 - Ordered Pyridazine Nanothreads through Selective Cycloaddition
AU - Dunning, Samuel G.
AU - Zhu, Li
AU - Chen, Bo
AU - Chariton, Stella
AU - Prakapenka, Vitali B.
AU - Somayazulu, Maddury
AU - Strobel, Timothy A.
N1 - Funding Information:
The authors thank Dr. Thomas Shiell for his assistance in XRD data collection. Portions of this work were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13) and HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation - Earth Sciences (EAR-1634415) and Department of Energy - GeoSciences (DE-FG02-94ER14466). HPCAT operations were supported by DOE-NNSA’s Office of Experimental Sciences. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02- 06CH11357.
Funding Information:
The authors acknowledge support from the U.S. Army Research Office under Grant W911NF-17-1-0604.
Funding Information:
The authors thank Dr. Thomas Shiell for his assistance in XRD data collection. Portions of this work were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13) and HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation - Earth Sciences (EAR-1634415) and Department of Energy - GeoSciences (DE-FG02-94ER14466). HPCAT operations were supported by DOE-NNSA's Office of Experimental Sciences. This research used resources of the Advanced Photon Source a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02- 06CH11357.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/2/9
Y1 - 2022/2/9
N2 - Nanothreads are one-dimensional nanomaterials composed of a primarily sp3 hydrocarbon backbone, typically formed through the compression of small molecules to high pressures. Although nanothreads have been synthesized from a range of precursors, controlling reaction pathways to produce atomically precise materials remains a difficult challenge. Here, we show how heteroatoms within precursors can serve as "thread-directing"groups by selecting for specific cycloaddition reaction pathways. By using a less-reactive diazine group within a six-membered aromatic ring, we successfully predict and synthesize the first carbon nanothread material derived from pyridazine (1,2-diazine, C4H4N2). Compared with previous nanothreads, the synthesized polypyridazine, shows a predominantly uniform chemical structure with exceptional long-range order, allowing for structural characterization using vibrational spectroscopy and X-ray diffraction. The results demonstrate how thread-directing groups can be used for reaction pathway control and the formation of chemically precise nanothreads with a high degree of structural order.
AB - Nanothreads are one-dimensional nanomaterials composed of a primarily sp3 hydrocarbon backbone, typically formed through the compression of small molecules to high pressures. Although nanothreads have been synthesized from a range of precursors, controlling reaction pathways to produce atomically precise materials remains a difficult challenge. Here, we show how heteroatoms within precursors can serve as "thread-directing"groups by selecting for specific cycloaddition reaction pathways. By using a less-reactive diazine group within a six-membered aromatic ring, we successfully predict and synthesize the first carbon nanothread material derived from pyridazine (1,2-diazine, C4H4N2). Compared with previous nanothreads, the synthesized polypyridazine, shows a predominantly uniform chemical structure with exceptional long-range order, allowing for structural characterization using vibrational spectroscopy and X-ray diffraction. The results demonstrate how thread-directing groups can be used for reaction pathway control and the formation of chemically precise nanothreads with a high degree of structural order.
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U2 - 10.1021/jacs.1c12143
DO - 10.1021/jacs.1c12143
M3 - Article
C2 - 35077643
AN - SCOPUS:85124167262
SN - 0002-7863
VL - 144
SP - 2073
EP - 2078
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 5
ER -