Electrostatic and Geometric Regulation of “Third Terminal” in Non‐Fullerene Acceptors for High‐Performance Organic Photovoltaics

S Shuhui Ding (State Key Laboratory and Institute of Elemento‐Organic Chemistry The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials Renewable Energy Conversion and Storage Center (RECAST) Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 China) Z Zheng Xu W Wenkai Zhao (Frontiers Science Center for New Organic Matter, Tianjin Key Lab for Rare Earth Materials and Applications, Renewable Energy Conversion and Storage Center (RECAST), School of Materials Science and Engineering, National Institute for Advanced Materials) Q Qiaorong Liu (State Key Laboratory and Institute of Elemento‐Organic Chemistry The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials Renewable Energy Conversion and Storage Center (RECAST) Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 China) Y Yu Zhang (Xiangya Hospital, Central South University Changsha China) Z Zhaoyang Yao (State Key Laboratory and Institute of Elemento-Organic Chemistry, The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, College of Chemistry) Y Yaxiao Guo (State Key Laboratory of Advanced Separation Membrane Materials School of Chemistry Tiangong University Tianjin China) G Guankui Long (Frontiers Science Center for New Organic Matter, Tianjin Key Lab for Rare Earth Materials and Applications, Renewable Energy Conversion and Storage Center (RECAST), School of Materials Science and Engineering, National Institute for Advanced Materials) C Chenxi Li (State Key Laboratory and Institute of Elemento-Organic Chemistry, The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, College of Chemistry) X Xiangjian Wan (State Key Laboratory and Institute of Elemento-Organic Chemistry, The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, College of Chemistry) Y Yongsheng Chen (Department of Neurosurgery The Tenth Affiliated Hospital Southern Medical University Dongguan China)

Abstract

Abstract Inspired by the dominant role of 2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene) malononitrile (INCN) terminal in regulating molecular packing, an innovative strategy to construct “third terminals” of non‐fullerene acceptors (NFAs) is proposed by introducing INIC‐mimicking motifs to molecular backbone center. Through delicate electrostatic and geometric regulation of INCN analogues (NQ, DCNQ, and TCNC), newly designed NFAs (CH56, CH57, and CH58) render not only an inverted distribution of molecular frontier orbitals, but also the substantial HOMO–LUMO overlap for CH56 while pronounced spatial separation for others. Especially, the puckered TCNC with the most LUMOs distribution yet minimal involvement in molecular packings drives CH58 to adopt a pseudo‐three‐dimensional (3D) packing network and inferior electron migration in sharp contrast to CH56. Moreover, the twisty CH57 and CH58 also exhibit unexpectedly quenched fluorescence due to the severe skeletal vibrations DCNQ and TCNC, further resulting in the large energy losses and poor photovoltaic performance. Finally, CH56‐based OSCs yield a surprising open‐circuit‐voltage of 1.007 V for binary devices and an excellent 20.16% efficiency for ternary devices. Our trials on “third terminal” has enabled the extensive exploration of novel architectures of NFAs beyond conventional structural paradigms.

Article Details

Volume / Issue Vol. 65, Issue 2
Published January 09, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (11)

S

Shuhui Ding

State Key Laboratory and Institute of Elemento‐Organic Chemistry The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials Renewable Energy Conversion and Storage Center (RECAST) Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 China

Z

Zheng Xu

W

Wenkai Zhao

Frontiers Science Center for New Organic Matter, Tianjin Key Lab for Rare Earth Materials and Applications, Renewable Energy Conversion and Storage Center (RECAST), School of Materials Science and Engineering, National Institute for Advanced Materials

Q

Qiaorong Liu

State Key Laboratory and Institute of Elemento‐Organic Chemistry The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials Renewable Energy Conversion and Storage Center (RECAST) Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 China

Y

Yu Zhang

Xiangya Hospital, Central South University Changsha China

Z

Zhaoyang Yao

State Key Laboratory and Institute of Elemento-Organic Chemistry, The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, College of Chemistry

Y

Yaxiao Guo

State Key Laboratory of Advanced Separation Membrane Materials School of Chemistry Tiangong University Tianjin China

G

Guankui Long

Frontiers Science Center for New Organic Matter, Tianjin Key Lab for Rare Earth Materials and Applications, Renewable Energy Conversion and Storage Center (RECAST), School of Materials Science and Engineering, National Institute for Advanced Materials

C

Chenxi Li

State Key Laboratory and Institute of Elemento-Organic Chemistry, The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, College of Chemistry

X

Xiangjian Wan

State Key Laboratory and Institute of Elemento-Organic Chemistry, The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, College of Chemistry

Y

Yongsheng Chen

Department of Neurosurgery The Tenth Affiliated Hospital Southern Medical University Dongguan China