Axially and Helically Chiral Cationic Radical Bicarbazoles: SOMO-HOMO Level Inversion and Chirality Impact on the Stability of Mono- and Diradical Cations

被引：62

作者：

Kasemthaveechok, Sitthichok ^{[1
]}

Abella, Laura ^{[2
]}

Jean, Marion ^{[3
]}

Cordier, Marie ^{[1
]}

Roisnel, Thierry ^{[1
]}

Vanthuyne, Nicolas ^{[3
]}

Guizouarn, Thierry ^{[1
]}

Cador, Olivier ^{[1
]}

Autschbach, Jochen ^{[2
]}

Crassous, Jeanne ^{[1
]}

Favereau, Ludovic ^{[1
]}

机构：

[1] Univ Rennes, F-35000 Rennes, France

[2] Univ Buffalo State Univ New York, Dept Chem, Buffalo, NY 14260 USA

[3] Aix Marseille Univ, F-13284 Marseille, France

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2020年 / 142卷 / 48期

基金：

美国国家科学基金会;

关键词：

LIGHT-EMITTING-DIODES; ELECTRONIC-STRUCTURE; ROOM-TEMPERATURE; BASIS-SETS; SPIN; MOLECULES; HELICENE; DESIGN; CONVERSION; VALENCE;

D O I：

10.1021/jacs.0c08948

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report persistent chiral organic mono- and diradical cations based on bicarbazole molecular design with an unprecedented stability dependence on the type of chirality, namely, axial versus helical. An unusual chemical stability was observed for sterically unprotected axial bicarbazole radical in comparison with monocarbazole and helical bicarbazole ones. Such results were experimentally and theoretically investigated, revealing an inversion in energy of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbital (HOMO) in both axial and helical bicarbazole monoradicals along with a subtle difference of electronic coupling between the two carbazole units, which is modulated by their relative dihedral angle and related to the type of chirality. Such findings allowed us to explore in depth the SOMO-HOMO inversion (SHI) in chiral radical molecular systems and provide new insights regarding its impact on the stability of organic radicals. Finally, these specific electronic properties allowed us to prepare a persistent, intrinsically chiral, diradical which notably displayed near-infrared electronic circular dichroism responses up to 1100 nm and almost degenerate singlet-triplet ground states with weak antiferromagnetic interactions evaluated by magnetometry experiments.

引用

页码：20409 / 20418

页数：10

共 73 条

[1] Diradicals [J].