A Heptacene Analogue Entailing a Quinoidal Benzodi[7]annulene (7/6/7 Ring) Core with a Tunable Configuration and Multiple Redox Properties. (20th March 2023)

• Record Type: Journal Article
• Authors: Huang, Yan‐Ying; Wu, Botao; Shi, Dandan; Liu, Dan; Meng, Wei; Ma, Junlong; Qin, Liyuan; Li, Cheng; Zhang, Guanxin; Zhang, Xi‐Sha; Zhang, Deqing
• Is Part Of: Angewandte Chemie. Volume 135:Number 17(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-03-20
• Subjects: 7/6/7 Ring -- Configuration Modulation -- Heptacenes -- Polymorphism -- Substituent Effects; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202300990
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Non‐benzenoid acenes containing heptagons have received increasing attention. We herein report a heptacene analogue containing a quinoidal benzodi[7]annulene core. Derivatives of this new non‐benzenoid acene were obtained through an efficient synthetic strategy involving an Aldol condensation and a Diels–Alder reaction as key steps. The configuration of this heptacene analogue can be modulated from a wavy to a curved one by just varying the substituents from a (triisopropylsilyl)ethynyl group to a 2, 4, 6‐triisopropylphenyl (Trip) group. When mesityl (Mes) groups are linked to the heptagons, the resulting non‐benzenoid acene displays polymorphism with a tunable configuration from a curved to a wavy one upon varying the crystallization conditions. In addition, this new non‐benzenoid acene can be oxidized or reduced by NOSbF6 or KC8 to the respective radical cation or radical anion. Compared with the neutral acene, the radical anion shows a wavy configuration and the central hexagon becomes aromatic. Abstract : Varying the substituents linked to the heptagons of a heptacene analogue containing a quinoidal benzodi[7]annulene core allows modulation of the configuration of this acene. When Mes groups are attached to the heptagons, the resulting acene displays polymorphism, with a tunable configuration ranging from a curved to a wavy one. This acene can also be oxidized or reduced by NOSbF6 or KC8 to the respective radical cation or radical anion.