Simultaneous Ring Contraction and Expansion Reaction: Electrosynthesis of Heterocycle‐Fused Fulleroids and Photovoltaic Application

• Published in: Angewandte Chemie International Edition Vol. 62; no. 25; pp. e202304321 - n/a
• Main Authors: Yin, Zheng‐Chun, Li, Mingjie, Niu, Chuang, Wang, Wei‐Feng, Liu, Wen‐Rui, Zhang, Qian‐Wen, Wang, Guan‐Wu
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 19-06-2023
• Edition: International ed. in English
• Subjects: Bromides; Chemical reactions; Configurations; Crystallography, X-Ray; Electrochemistry; Electrosynthesis; Fullerene; Fullerenes; Fullerenes - chemistry; Fulleroid; Halogens; Oxidation; Oxygen; Photovoltaic cells; Photovoltaics; Regioselectivity; Ring Contraction; Ring Expansion; Solar cells; Stereoisomerism; Stereoisomers; Trifluoroacetic acid; Fullerene; Electrosynthesis; Ring Expansion; Fulleroid; Ring Contraction
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202304321

Simultaneous electrochemical ring contraction and expansion reactions remain unexplored to date. Herein, the reductive electrosynthesis of heterocycle‐fused fulleroids from fullerotetrahydropyridazines and electrophiles in the presence of a trace amount of oxygen has been achieved with concurrent ring contraction and ring expansion. When trifluoroacetic acid and alkyl bromides are employed as electrophiles, heterocycle‐fused fulleroids with a 1,1,2,6‐configuration are regioselectively formed. In contrast, heterocycle‐fused fulleroids with a 1,1,4,6‐configuration are regioselectively produced as two separable stereoisomers if phthaloyl chloride is used as the electrophile. The reaction proceeds through multiple steps of electroreduction, heterocycle ring‐opening, oxygen oxidation, heterocycle contraction, fullerene cage expansion, and nucleophilic addition. The structures of these fulleroids have been determined by spectroscopic data and single‐crystal X‐ray diffraction analyses. The observed high regioselectivities have been rationalized by theoretical calculations. Representative fulleroids have been applied in organic solar cells as the third component and exhibit good performance.
The electrochemically triggered simultaneous ring contraction and expansion reaction of fullerotetrahydropyridazines with electrophiles in the presence of a trace amount of oxygen affords pyrazoline‐fused fulleroids with unprecedented 1,1,2,6‐ or 1,1,4,6‐addition patterns.