Citation: Hongchao Wang, Wei Hao, Haowei Wu, Qianyu Ding, Yu Wei, Hu Zhao, Shuzhou Li, Hanying Li, Jia Zhu. Rational design of n-type organic thermoelectric materials: Insights from C_nBTBT–F_mTCNQ charge-transfer complexes[J]. Chinese Chemical Letters, ;2026, 37(2): 111933. doi: 10.1016/j.cclet.2025.111933 shu

Rational design of n-type organic thermoelectric materials: Insights from C_nBTBT–F_mTCNQ charge-transfer complexes

Hongchao Wang ^{a, b, 1} ,
Wei Hao ^{c, 1,*,} ,
Haowei Wu ^{a, d} ,
Qianyu Ding ^{a, b} ,
Yu Wei ^{a, d} ,
Hu Zhao ^e ,
Shuzhou Li ^f ,
Hanying Li ^c ,
Jia Zhu ^{a, b, *,}

a.
Laboratory of Theoretical and Computational Nanoscience, National Center for Nanoscience and Technology, Chinese Academy of Sciences, Beijing 100190, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, International Research Center for X Polymers, ZJU-YST Joint Research Center for Fundamental Science, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
d.
College of Chemistry, Key Laboratory of Theoretical & Computational Photochemistry of Ministry of Education, Beijing Normal University, Beijing 100875, China
e.
School of Physics and Astronomy, Beijing Normal University, Beijing 100875, China
f.
School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore

hao_wei@zju.edu.cn

zhujia@nanoctr.cn

Received Date: 14 June 2025
Revised Date: 27 September 2025
Accepted Date: 30 September 2025
Available Online: 1 October 2025

Figures(3)

Charge-transfer complexes (CTCs) have emerged as promising n-type organic thermoelectric (TE) materials due to their inherent high electrical conductivity and tunable transport polarities. In this study, we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes (C_nBTBT, n = 4, 8, 12) as donors and fluorinated derivatives of tetracyanoquinodimethane (F_mTCNQ, m = 0, 2, 4) as acceptors, aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure–property relationships. Our calculation results, based on the Boltzmann transport equation and deformation potential theory, reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties. Notably, the C_nBTBT–F_mTCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics, particularly C₄BTBT–F₄TCNQ, which achieves an excellent power factor of 671 µW cm^-1 K^-2 at an optimal charge carrier concentration. Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.
- Charge-transfer complexes,
- Organic thermoelectric,
- Power factor,
- First-principles calculations,
- Structure–property relationships
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Rational design of n-type organic thermoelectric materials: Insights from CnBTBT–FmTCNQ charge-transfer complexes

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通讯作者: 陈斌, bchen63@163.com

Rational design of n-type organic thermoelectric materials: Insights from C_nBTBT–F_mTCNQ charge-transfer complexes