Control over electronic structures of organic diradicaloids via precise B/O-heterocycle fusion  

作　　者：Xinyu Tian Jiaxiang Guo Zeyi Li Shihou Sheng Tianyu Zhang Xianfei Li Chuandong Dou 

机构地区：[1]State Key Laboratory of Supramolecular Structure and Materials,College of Chemistry,Jilin University,Changchun 130012,China [2]Gastrointestinal and Colorectal Surgery,Third Hospital of Jilin University,Changchun 130012,China

出　　处：《Chinese Chemical Letters》2025年第1期306-311,共6页中国化学快报(英文版)

基　　金：supported by National Natural Science Foundation of China(Nos.52373182 and 22175074);Jilin Scientific and Technological Development Program(No.20220101054JC);Department of Education of Jilin Province(No.JJKH20221046KJ)。

摘　　要：Diradicaloid polycyclic hydrocarbons(PHs)own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics.Herein,we disclose precise fusion of B/O-heterocycles onto PHs for control over their electronic structures and diradical properties.We designed and synthesized four B/O-containing diradicaloid isomers that feature the fluoreno[3,2-b]fluorene and fluoreno[2,1-a]fluoreneπ-skeletons,respectively.The precise B/O-heterocycle fusion modes along with the changed conjugation patterns lead to their modulated electronic structures and properties,such as diradical and aromatic structures,energy levels and band gaps,as well as magnetic,electrochemical and photophysical properties.Notably,the mode A may decrease the open-shell extent,whereas the mode B can enhance the diradical nature,leading to their well-tuned diradical characters in the range of0.46-0.70.Moreover,the mode A stabilizes the LUMOs and the mode B obviously increases the HOMO levels,which are remarkably contributed by the B and O atoms,respectively,further giving rise to the decreased band gaps and redshifted absorptions.This study clearly illustrates the electronic effects of B/O-heterocycle fusion on PHs and gains insight into B/O-type organic diradicaloids.These findings will provide an important guideline for the design of more fascinating heteroatom-containing diradicaloids.

关 键 词：Organic diradicaloids BORON Electronic structure Quinoidal conjugation AROMATICITY 

分 类 号：O62[理学—有机化学]