JEFFREY M. FARRELLMuetzel, CarinaCarinaMuetzelBialas, DavidDavidBialasRudolf, MaximilianMaximilianRudolfMenekse, KaanKaanMenekseKrause, Ana-MariaAna-MariaKrauseStolte, MatthiasMatthiasStolteWuerthner, FrankFrankWuerthner2022-05-272022-05-272019https://www.scopus.com/inward/record.uri?eid=2-s2.0-85066871991&doi=10.1021%2fjacs.9b04675&partnerID=40&md5=c026ebf72da5b3c2a1831e6d07371e47https://scholars.lib.ntu.edu.tw/handle/123456789/612091Boron-doping has long been recognized as a promising LUMO energy-lowering modification of graphene and related polycyclic aromatic hydrocarbons (PAHs). Unfortunately, synthetic difficulties have been a significant bottleneck for the understanding, optimization, and application of precisely boron-doped PAHs for optoelectronic purposes. Herein, a facile one-pot hydroboration electrophilic borylation cascade/dehydrogenation approach from simple alkene precursors is coupled with postsynthetic B-substitution to give access to ten ambient-stable core- and periphery-tuned boron-doped PAHs. These include large hitherto unknown doubly boron-doped analogues of anthanthrene and triangulene. Crystallographic, optical, electrochemical, and computational studies were performed to clarify the effect of boron-doped PAH shape, size, and structure on optoelectronic properties. Our molecular tuning allowed the synthesis of molecules exhibiting visible-range absorption, near-unity fluorescence quantum yields, and, to our knowledge, the most facile electrochemical reductions of any reported ambient-stable boron-doped PAHs (corresponding to LUMO energy levels as low as fullerenes). Finally, our study describes the first implementation of a precise three-coordinate boron-substituted PAH as an acceptor material in organic solar cells with power conversion efficiencies (PCEs) of up to 3%. ? 2019 American Chemical Society.Boron; Electrolytic reduction; Mineral oils; Organic solar cells; Solar cells; Synthesis (chemical); Computational studies; Electrochemical reductions; Fluorescence quantum yield; LUMO energy levels; Optoelectronic properties; Polycyclic aromatic hydrocarbons (PAHS); Power conversion efficiencies; Visible range; Polycyclic aromatic hydrocarbons; alkene; anthanthrene derivative; boron; fullerene derivative; polycyclic aromatic hydrocarbon derivative; triangulene derivative; unclassified drug; absorption; Article; borylation; chemical structure; controlled study; dehydrogenation; electrochemical analysis; electrophilicity; fluorescence quantum yield; hydroboration; mass spectrometry; one pot synthesis; oxidation reduction reaction; proton nuclear magnetic resonance; quantum yield; X ray crystallographyjournal article10.1021/jacs.9b046752-s2.0-85066871991