Agrawal Abhijeet R, Shioukhi Israa, Deree Yinon, Bogoslavsky Benny, Shalev Ori, Hoffman Roy, Gidron Ori
Institute of Chemistry and the Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Jerusalem, 9190401, Israel.
The Metabolic Profiling Unit, The Core Research Facility, The Faculty of Medicine, The Hebrew University of Jerusalem, Jerusalem, Israel.
Angew Chem Int Ed Engl. 2025 Aug 11;64(33):e202510423. doi: 10.1002/anie.202510423. Epub 2025 Jun 20.
The extent of helicity in nonplanar polyaromatic materials affects their electronic, optical and chiroptical properties. However, controlling helicity in different systems typically requires different multistep synthetic approaches for each target compound, often with significant complexity, thereby limiting its applicability. Here, we introduce a helical synthon, isobenzofuranophane, with either a short or long tether, which enables late-stage helicity induction and control in aromatic frameworks. We demonstrate the applicability of this synthon by reacting it with a [5]helicene aryne precursor, where both the handedness and helicene pitch are remotely-controlled by the tether length, directly affecting the (chiro)optical properties of the helicene. The X-ray structures support these findings with up to 35° torsion for a single benzene ring, demonstrating the potential of isobenzofuranophane to induce significant curvature to polyaromatic molecules.
非平面多芳族材料中的螺旋度程度会影响其电子、光学和手性光学性质。然而,在不同体系中控制螺旋度通常需要针对每种目标化合物采用不同的多步合成方法,且往往具有显著的复杂性,从而限制了其适用性。在此,我们引入了一种螺旋合成子——异苯并呋喃并环,其具有短链或长链连接基,能够在芳香族骨架中实现后期螺旋度诱导和控制。我们通过使其与一个[5]螺烯芳炔前体反应来证明这种合成子的适用性,其中手性和螺烯螺距可通过连接基长度进行远程控制,直接影响螺烯的(手性)光学性质。X射线结构支持了这些发现,单个苯环的扭转角度可达35°,证明了异苯并呋喃并环使多芳族分子产生显著曲率的潜力。