Demachkie Isabella S, Miller Michael P, Warren Gabrielle I, Barker Joshua E, Strand Eric T, Zakharov Lev N, Haley Michael M
Department of Chemistry and Biochemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon, 97403-1253, United States.
Center for Advanced Materials Characterization at Oregon (CAMCOR), University of Oregon, Eugene, Oregon, 97403-1433, United States.
Angew Chem Int Ed Engl. 2025 Feb 24;64(9):e202420989. doi: 10.1002/anie.202420989. Epub 2024 Dec 16.
Herein we report the synthesis and characterization of four donor/acceptor-fused s-indacenes via the late-stage oxidation of a family of unsymmetrical benzofuran/benzothiophene-s-indacene regioisomers. A thorough study of their properties through experimental and computational analysis has revealed the effect of asymmetry on the molecular properties associated with antiaromaticity, as well as a strong correlation between antiaromaticity and intramolecular charge transfer (ICT). The strength of the charge transfer depends on the fusion orientation of the donor and acceptor motifs relative to the s-indacene core. The two most antiaromatic oxidized isomers exhibit strong evidence of ICT with 30 and 40 nm solvatochromic shifts.
在此，我们报道了通过一族不对称苯并呋喃/苯并噻吩-s-茚并萘区域异构体的后期氧化反应合成并表征了四种供体/受体稠合的s-茚并萘。通过实验和计算分析对其性质进行的深入研究揭示了不对称性对与反芳香性相关的分子性质的影响，以及反芳香性与分子内电荷转移（ICT）之间的强相关性。电荷转移的强度取决于供体和受体基序相对于s-茚并萘核心的稠合取向。两种反芳香性最强的氧化异构体表现出ICT的有力证据，溶剂化显色位移分别为30和40 nm。
