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optimized structure approximately agrees with the X-ray analysis
result and appears suitable for the photocyclization reaction. The
close atomic contacts between N2eH7 (2.36 nm) and N3eH1
(2.83 nm) atoms were also reproduced in this DFT calculation,
which suggests specific stabilization of the reactive conformation
with these non-covalent interactions.
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A new triangular terarylenes has been designed and synthesized
that contains specific intramolecular interactions between the
central and side units that facilitate the photochromic response.
The photocyclization quantum yield of compound 1a in hexane was
as high as 0.83, which is close to that of one of the most sensitive
photochromic compound so far reported. X-ray crystal structure
analysis revealed that compound 1a is in the photoreactive
conformation with quasi-C2 symmetry. Variable temperature 1H
NMR spectroscopy, crystal structure and DFT calculations suggest
the possibility of weak intramolecular hydrogen bonding interac-
tions in the new triangular terarylene.
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Acknowledgments
The authors thank Mr. S. Katao and Mrs. Y. Nishikawa, the
Technical Staffs of NAIST for X-ray crystallographic analysis and
mass spectroscopic measurements. This work was partly supported
by Grant-in-Aids for Scientific Research on Priority Areas, “Photo-
chromism” from the Ministry of Education, Culture, Sports, Science
and Technology (MEXT) of Japan.
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chromic bisarylindenone and its acetal: achievement of large cyclization
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