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Chemical Reduction of a Nanosized [6]Cyclo‐2,7‐naphthylene Macrocycle
Author(s) -
Zhou Zheng,
Wei Zheng,
Ikemoto Koki,
Sato Sota,
Isobe Hiroyuki,
Petrukhina Marina A.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202100942
Subject(s) - chemistry , crown ether , ion , crystallography , alkali metal , solvent , ether , organic chemistry
Chemical reduction of a naphthylene macrocycle, [6]cyclo‐2,7‐naphthylene ([6]CNAP, 1 ), with alkali metals, Li and K, revealed the accessibility of the doubly‐reduced state of 1 . The macrocyclic 1 2− anion was isolated in different coordination environments and crystallographically characterized. The single‐crystal X‐ray diffraction confirmed the formation of contact‐ion complexes with one Li + and two K + ions in THF, and a “naked” dianion in the solvent‐separated ion product with K + ions in the presence of 18‐crown‐6 ether. The detailed structural analysis of 1 2− showed that the π‐conjugation over the biaryl linkages between naphthylene panels were enhanced upon two‐fold reduction, which was rationally explained by theoretical calculations.

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