Charging OBO-Fused Double [5]Helicene with Electrons

Chemical reduction of OBO-fused double[5]helicene with Group 1 metals (Na and K) has been investigated for the first time. Two doubly-reduced products have been isolated and structurally characterized by single-crystal X-ray diffraction, revealing a solvent-separated ion triplet (SSIT) with Na⁺ ions and a contact-ion pair (CIP) with K⁺ ion. As the key structural outcome, the X-ray crystallographic analysis discloses the consequences of adding two electrons to the double helicene core in the SSIT without metal binding and reveals the preferential binding site in the CIP with K⁺ counterions. In both products, an increase in the twisting of the double helicene core upon charging was observed. The negative charge localization at the central core has been identified by theoretical calculations, which are in full agreement with X-ray crystallographic and NMR spectroscopic results. Notably, it was confirmed that the two-electron reduction of OBO-fused double[5]helicene is reversible.