Strong Acceptor Annulation Enables Control of Electronic Structure and Spin Configuration in Donor-Acceptor Conjugated Polymers

被引:4
作者
Eedugurala, Naresh [1 ]
Steelman, Michael E. [1 ]
Mahalingavelar, Paramasivam [1 ]
Adams, Daniel J. [1 ]
Mayer, Kevin S. [1 ]
Liu, Chih-Ting [1 ]
Benasco, Anthony [1 ]
Ma, Guorong [1 ]
Gu, Xiaodan [1 ]
Bowman, Michael K. [2 ]
Azoulay, Jason D. [1 ,3 ]
机构
[1] Univ Southern Mississippi, Sch Polymer Sci & Engn, Hattiesburg, MS 39406 USA
[2] Univ Alabama, Dept Chem & Biochem, Tuscaloosa, AL 35487 USA
[3] Georgia Inst Technol, Sch Chem & Biochem, Sch Mat Sci & Engn, Atlanta, GA 30332 USA
基金
美国国家科学基金会;
关键词
QUANTUM-CHEMICAL APPROACH; OLIGOMERS; STATE;
D O I
10.1021/acs.chemmater.2c03548
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Open-shell conjugated polymers (CPs) offer new opportunities to integrate the spin degree of freedom within emerging technologies. Central to their realization are strong acceptors that stabilize unpaired spins within the x-conjugated backbones. Here, we demonstrate a high-spin CP composed of alternating benzo[1,2-b:4,5-b ']dithiophene donors and a new, strongly electron-withdrawing 6,7,8,9-tetrachloro-[1,2,5]thiadiazolo[3,4-b]phenazine acceptor. A comparative study with a 6,7dimethyl-[1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ) acceptor demonstrates that annulation and chlorination of the TQ framework facilitates a transition between closed-shell aromatic and high-spin quinoidal forms. This is accompanied by a concomitant reduction of the bandgap, high electron affinity, delocalization of spin density, and n-type conduction. These insights enable access to a broader range of open-shell CPs and the manipulation of important properties such as topology, exchange interactions, and carrier polarity.
引用
收藏
页码:3115 / 3123
页数:9
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