Tunable Low-LUMO Boron-Doped Polycyclic Aromatic Hydrocarbons by General One-Pot C–H Borylations
journal contributionposted on 20.05.2019, 18:37 authored by Jeffrey M. Farrell, Carina Mützel, David Bialas, Maximilian Rudolf, Kaan Menekse, Ana-Maria Krause, Matthias Stolte, Frank Würthner
Boron-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%.
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boron-doped analoguesoptoelectronic purposesboron-doped PAHsLUMO energy-lowering modificationoptoelectronic propertiespower conversion efficienciesambient-stable boron-doped PAHsPCEthree-coordinate boron-substituted PAHpostsynthetic B-substitutionambient-stable coreelectrochemical reductionsTunable Low-LUMO Boron-Doped Polycyclic Aromatic Hydrocarbonsperiphery-tuned boron-doped PAHsboron-doped PAH shapeLUMO energy levelsnear-unity fluorescence quantum yieldsacceptor materialalkene precursorsvisible-range absorption