Crystalline Diradical Dianions of Pyrene-Fused Azaacenes

被引：19

作者：

Chen, Chao ^{[1
]}

Ruan, Huapeng ^{[1
]}

Feng, Zhongtao ^{[1
]}

Fang, Yong ^{[1
]}

Tang, Shuxuan ^{[1
]}

Zhao, Yue ^{[1
]}

Tan, Gengwen ^{[2
]}

Su, Yuanting ^{[2
]}

Wang, Xinping ^{[1
]}

机构：

[1] Nanjing Univ, Collaborat Innovat Ctr Adv Microstruct, Sch Chem & Chem Engn, State Key Lab Coordinat Chem,Jiangsu Key Lab Adv, Nanjing 210023, Peoples R China

[2] Soochow Univ, Coll Chem Chem Engn & Mat Sci, Suzhou 215123, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 29期

基金：

中国国家自然科学基金; 国家重点研发计划;

关键词：

azaacenes; crystal structure; dianions; diradicals; pyrenes; BIS(TRIARYLAMINE) DICATIONS; RADICAL IONS; CHEMISTRY; OLIGOTHIOPHENES; BIRADICALS; CHARACTER;

D O I：

10.1002/anie.202001842

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Although diradicals and azaacenes have been greatly attractive in fundamental chemistry and functional materials, the isolable diradical dianions of azaacenes are still unknown. Herein, we describe the first isolation of pyrene-fused azaacene diradical dianion salts [(18-c-6)K(THF)(2)](+)[(18-c-6)K](+).1(2-..) and [(18-c-6)K(THF)](2+).2(2-..) by reduction of the neutral pyrene-fused azaacene derivatives 1 and 2 with excess potassium graphite in THF in the presence of 18-crown-6. Their electronic structures were investigated by various experiments, in conjunction with theoretical calculations. It was found that both dianions are open-shell singlets in the ground state and their triplet states are thermally readily accessible owing to the small singlet-triplet energy gap. This work provides the first examples of crystalline diradical dianions of azaacenes with considerable diradical character.

引用

页码：11794 / 11799

页数：6

共 46 条

[41] Isolable Radical Ions of Main-Group Elements: Structures, Bonding and Properties [J].