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In this study, for the first time, two new GDAs, DYF\u2010V and DY2F\u2010V are designed and synthesized for OSC operation, by connecting one vinylene linker with the mono\u2010\/di\u2010fluorinated end group on two Y\u2010series monomers, respectively. After fluorination, both DYF\u2010V and DY2F\u2010V exhibit bathochromic absorption and denser packing modes due to the stronger intramolecular charge transfer effect and torsion\u2010free backbones. Through precise fluorination, the DYF\u2010V\u2010based devices exhibit the highest performance of 18.63% among the GDA\u2010based OSCs, outperforming its non\u2010fluorinated counterpart, DY\u2010V\u2010based ones (16.53%). Theoretical and morphological results demonstrate that proper fluorination in DYF\u2010V\u2010based devices strengthens intra\/intermolecular interactions for enhanced crystallinity, superior phase segregation, and less energy disorder, which is beneficial for fast exciton dissociation, rapid carrier transport, and suppressed charge recombination. The work demonstrates that proper fluorination on GDAs with rigid coplanar backbones is effective for broader photon harvesting, stronger packing, and robust stability in GDA\u2010based OSCs.<\/jats:p>","DOI":"10.1002\/advs.202410826","type":"journal-article","created":{"date-parts":[[2025,1,21]],"date-time":"2025-01-21T02:10:27Z","timestamp":1737425427000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Coplanar Dimeric Acceptors with Bathochromic Absorption and Torsion\u2010Free Backbones through Precise Fluorination Enabling Efficient Organic Photovoltaics with 18.63% Efficiency"],"prefix":"10.1002","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6829-2404","authenticated-orcid":false,"given":"Wei","family":"Liu","sequence":"first","affiliation":[{"name":"Guangdong\u2010Hong Kong Joint Laboratory for Carbon Neutrality Jiangmen Laboratory of Carbon Science and Technology  Jiangmen Guangdong 529199 P. 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