The chemical reduction of a corannulene-based molecular nanographene, C 76 H 64 (1), with Na metal in the presence of 18-crown-6 afforded the doubly-reduced state of 1. This reduction provokes a distortion of the helicene core and has a significant impact on the aromaticity of the system.
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Abstract The chemical reduction of π‐conjugated bilayer nanographene
1 (C138H120) with K and Rb in the presence of 18‐crown‐6 affords [K+(18‐crown‐6)(THF)2][{K+(18‐crown‐6)}2(THF)0.5][C138H1223−] (2 ) and [Rb+(18‐crown‐6)2][{Rb+(18‐crown‐6)}2(C138H1223−)] (3 ). Whereas K+cations are fully solvent‐separated from the trianionic core thus affording a “naked”1.3 −anion, Rb+cations are coordinated to the negatively charged layers of1.3 −. According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site‐specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction‐induced site‐specific hydrogenation provokes dramatic changes in the (electronic) structure of1 as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers. -
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Abstract The chemical reduction of π‐conjugated bilayer nanographene
1 (C138H120) with K and Rb in the presence of 18‐crown‐6 affords [K+(18‐crown‐6)(THF)2][{K+(18‐crown‐6)}2(THF)0.5][C138H1223−] (2 ) and [Rb+(18‐crown‐6)2][{Rb+(18‐crown‐6)}2(C138H1223−)] (3 ). Whereas K+cations are fully solvent‐separated from the trianionic core thus affording a “naked”1.3 −anion, Rb+cations are coordinated to the negatively charged layers of1.3 −. According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site‐specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction‐induced site‐specific hydrogenation provokes dramatic changes in the (electronic) structure of1 as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers.
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