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  1. Anionic forms of a macrocyclic cyclophane were crystallized by treating the neutral hydrocarbon with alkali metals (Li, Na and K). The di-anions show decreased bond-length alternation, consistent with global aromaticity, whereas the anti-aromatic tetra-anion has a low-symmetry geometry.

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    Free, publicly-accessible full text available December 13, 2024
  2. Free, publicly-accessible full text available October 1, 2024
  3. Stepwise deprotonation of truxene with alkali metals affords truxenyl anions with different charges, exhibiting core curvature dependence on charge and metal binding. UV-vis and PL studies reveal charge-dependent optical properties, which is further supported by DFT calculations.

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    Free, publicly-accessible full text available November 22, 2024
  4. 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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  5. The chemical reduction of a π-expanded COT derivative, octaphenyltetrabenzocyclooctatetraene (1), with lithium or sodium metals in the presence of secondary ligands affords a new doubly-reduced product (1 TR 2− ). The X-ray diffraction study revealed a reductive core rearrangement accompanied by the formation of a single C–C bond and severe twist of the central tetraphenylene core. The reversibility of two-electron reduction and core transformation is further confirmed by NMR spectroscopy and DFT calculations. 
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    One-electron reduction of bowl-shaped indenocorannulene, C 26 H 12 , with Rb metal in THF affords [{Rb + (18-crown-6)} 2 (C 26 H 12 –C 26 H 12 ) 2− ]·4THF, as confirmed by single-crystal X-ray diffraction. The product consists of a dimeric σ-bonded dianion (C–C, 1.568(7) Å) having two endo -η 6 coordinated {Rb + (18-crown-6)} moieties (Rb–C, 3.272(4)–3.561(4) Å). The (C 26 H 12 –C 26 H 12 ) 2− dimer represents the first crystallographically confirmed example of spontaneous coupling for indenocorannulene monoanion radicals, C 26 H 12 ˙ − . Comprehensive theoretical investigation of the new dimer confirms the single σ-bond character of the linker and reveals a significant increase of both thermodynamic and kinetic stability of [σ-(C 26 H 12 ) 2 ] 2− in comparison with analogues formed by such π-bowls as corannulene and its dibenzo-derivative. The in-depth computational analysis and direct comparison of the series demonstrates the effect of curvature on radical coupling processes, allowing control over stability and reactivity of bowl-shaped π-radicals. 
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  8. Abstract

    We report a facile synthesis of diindeno‐fused dibenzo[a,h]anthracene derivatives (DIDBA‐2Cl,DIDBA‐2Ph, andDIDBA‐2H)with different degrees of non‐planarity using three substituents (chloro, phenyl, and hydrogen) of various sizes. The planarization of their cores, as evidenced by the decreased end‐to‐end torsional angles, was confirmed by X‐ray crystallography. Their enhanced energy gaps with twisting were investigated by a combination of spectroscopic and electrochemical methods with density functional theory, which showed a transition from singlet open‐shell to closed‐shell configuration. Moreover, their doubly reduced states,DIDBA‐2Ph2−andDIDBA‐2H2−, were achieved by chemical reduction. The structures of dianions were identified by X‐ray crystallographic analysis, which elucidated that the electron charging further distorted the backbones. The electronic structure of the dianions was demonstrated by experimental and theoretical approaches, suggesting decreased energy gaps with larger non‐planarity, different from the neutral species.

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