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Title
Japanese: 
English:Narrower HOMO-LUMO Gap Attained by Conformational Switching through Peripheral Polyarylation in 1,4,5,8-Tetraaza-9,10-Anthraquinodimethan 
Author
Japanese: T. Suzuki, Y. Ishigaki, K. Sugawara, Y. Umezawa, R. Katoono, A. Shimoyama, Y. Manabe, K. Fukase, 福島 孝典.  
English: T. Suzuki, Y. Ishigaki, K. Sugawara, Y. Umezawa, R. Katoono, A. Shimoyama, Y. Manabe, K. Fukase, T. Fukushima.  
Language English 
Journal/Book name
Japanese: 
English:Tetrahedron 
Volume, Number, Page Volume 74    Issue 18    Page 2239-2244
Published date May 18, 2018 
Publisher
Japanese: 
English: 
Conference name
Japanese: 
English: 
Conference site
Japanese: 
English: 
Official URL https://www.sciencedirect.com/science/article/pii/S0040402018303065
 
DOI https://doi.org/10.1016/j.tet.2018.03.041
Abstract 2,3,6,7,11,11,12,12-Octaphenyl-1,4,5,8-tetraaza-9,10-anthraquinodimethane was prepared as a sterically hindered molecule from 2,3,6,7-tetraphenyl-1,4,5,8-tetraaza-9,10-anthraquinone via bis(dibromomethylene) derivative through the quadruple Suzuki-Miyaura coupling reaction. An X-ray analysis revealed that steric repulsion is relieved mainly by twisting the exomethylene bonds, which is less common deformation for hindered quinodimethanes. According to the DFT calculations, the folded geometry with bent exomethylene bonds is the metastable conformer, and thus the nitrogen atoms at peri-positons and polyaryl substituents induce novel switching for the preferred geometry of 9,10-anthraquinodimethane skeleton from the common bent form to the twisted form, which causes a decrease in the HOMO-LUMO-gap energy by ca. 1 eV.

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