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Herein, a new type of central core of nonaromatic thianthrene is explored firstly, affording an exotic but structurally tailorable molecular platform for acceptor design. A unique puckered rather than planar conformation of central core is adopted, caused by the 4n \u03c0e\n                    <jats:sup>\u2212<\/jats:sup>\n                    feature, great ring strain and largely the insufficient p\u2013\u03c0 orbital overlap of lone pair on sulfur of thianthrene and coterminous benzene planes. As a result, the absorption of thianthrene\u2010based acceptors (CS1, CS2, and CS3) shows unexpected blue shift comparing to the phenazine\u2010based counterpart (CH20), regardless of the intrinsically strong electron\u2010donating characteristic of low valence sulfur atoms. Even so, the desired molecular packing and fibrillary film morphology, assisted by the suitable chlorination on thianthrene, still contribute to the best device efficiency of 19.0% based on D18:CS2 blends. Such novel work renders an underdeveloped NFA platform with the potentials for achieving PCE of over 20%.\n                  <\/jats:p>","DOI":"10.1002\/anie.202421289","type":"journal-article","created":{"date-parts":[[2025,3,26]],"date-time":"2025-03-26T03:07:13Z","timestamp":1742958433000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Highly Efficient Acceptors with a Nonaromatic Thianthrene Central Core for Organic Photovoltaics"],"prefix":"10.1002","volume":"64","author":[{"given":"Zheng","family":"Xu","sequence":"first","affiliation":[{"name":"State Key Laboratory and Institute of Elemento\u2010Organic Chemistry The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials Renewable Energy Conversion and Storage Center (RECAST) College of Chemistry Nankai University  Tianjin 300071 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