TY - JOUR
T1 - Mechanochromism, Twisted/Folded Structure Determination, and Derivatization of (N-Phenylfluorenylidene)acridane
AU - Matsuo, Yutaka
AU - Wang, Ya
AU - Ueno, Hiroshi
AU - Nakagawa, Takafumi
AU - Okada, Hiroshi
N1 - Funding Information:
This work was also supported by Grants-in-Aid for Scientific Research (JSPS KAKENHI Grant Numbers JP15H05760, JP16H04187, and JP17K19116) from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT), Japan. The computations were performed at the Research Center for Computational Science, Okazaki, Japan.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/6/24
Y1 - 2019/6/24
N2 - (N-Phenylfluorenylidene)acridane (Ph-FA) compounds with electron-withdrawing and -donating substituents (H, MeO, Ph, NO2, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N-aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p-NO2-C6H4-FA could be crystallographically characterized, which enabled the charge transfer from the electron-donating acridane moiety to the electron-accepting fluorenylidene moiety to be understood. Ground-state mechanochromism, thermochromism, vapochromism, and proton-induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph-FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors.
AB - (N-Phenylfluorenylidene)acridane (Ph-FA) compounds with electron-withdrawing and -donating substituents (H, MeO, Ph, NO2, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N-aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p-NO2-C6H4-FA could be crystallographically characterized, which enabled the charge transfer from the electron-donating acridane moiety to the electron-accepting fluorenylidene moiety to be understood. Ground-state mechanochromism, thermochromism, vapochromism, and proton-induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph-FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors.
KW - aromatic enes
KW - conformers
KW - mechanochromism
KW - nitrogen heterocycles
KW - overcrowded alkenes
UR - http://www.scopus.com/inward/record.url?scp=85066082983&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85066082983&partnerID=8YFLogxK
U2 - 10.1002/anie.201902636
DO - 10.1002/anie.201902636
M3 - Article
C2 - 30983037
AN - SCOPUS:85066082983
VL - 58
SP - 8762
EP - 8767
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 26
ER -