Distance-Selected Topochemical Dehydro-Diels-Alder Reaction of 1,4-Diphenylbutadiyne toward Crystalline Graphitic Nanoribbons.
J Am Chem Soc
; 142(41): 17662-17669, 2020 Oct 14.
Article
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| MEDLINE
| ID: mdl-32900188
ABSTRACT
Solid-state topochemical polymerization (SSTP) is a promising method to construct functional crystalline polymeric materials, but in contrast to various reactions that happen in solution, only very limited types of SSTP reactions are reported. Diels-Alder (DA) and dehydro-DA (DDA) reactions are textbook reactions for preparing six-membered rings in solution but are scarcely seen in solid-state synthesis. Here, using multiple cutting-edge techniques, we demonstrate that the solid 1,4-diphenylbutadiyne (DPB) undergoes a DDA reaction under 10-20 GPa with the phenyl as the dienophile. The crystal structure at the critical pressure shows that this reaction is "distance-selected". The distance of 3.2 Å between the phenyl and the phenylethynyl facilitates the DDA reaction, while the distances for other DDA and 1,4-addition reactions are too large to allow the bonding. The obtained products are crystalline armchair graphitic nanoribbons, and hence our studies open a new route to construct the crystalline carbon materials with atomic-scale control.
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01-internacional
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MEDLINE
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En
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J Am Chem Soc
Año:
2020
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Article