Summa Francesco F, Zanasi Riccardo, Đorđević Slađana, Radenković Slavko, Monaco Guglielmo
Dipartimento di Chimica e Biologia "A. Zambelli", University of Salerno, Fisciano, 84084, Italy.
University of Kragujevac, Faculty of Science, 34000, Kragujevac, Serbia.
Chemphyschem. 2024 Sep 16;25(18):e202400342. doi: 10.1002/cphc.202400342. Epub 2024 Jul 16.
Some years ago, Jishan Wu reported the synthesis of 8MC and 10MC, two homologues of the cyclopenta-ring-fused oligo(m-phenylene) macrocycles mMC, each behaving as an annulene-within-an-annulene (AWA). This was a surprising result as the AWA behavior is rare. Both molecules have a partial polyradical character, enforced by the quest for restoring some aromatic character of benzene rings. However, that restoration brings back some coupling between the two annulenes. Indeed, we found that the geometry and the magnetically induced currents indicate that, while 8MC does have an AWA character, this is not the case of the larger 10MC. Limitations of the design strategy of AWA molecules should be taken into account in future attempts to prepare novel large coronenes.
几年前，吴季山报道了环戊环稠合的低聚（间亚苯基）大环化合物mMC的两种同系物8MC和10MC的合成，它们各自表现为环中环（AWA）。这是一个令人惊讶的结果，因为AWA行为很罕见。这两种分子都具有部分多自由基特征，这是由于恢复苯环的一些芳香性的需求所导致的。然而，这种恢复使两个环之间产生了一些耦合。实际上，我们发现几何结构和磁诱导电流表明，虽然8MC确实具有AWA特征，但较大的10MC并非如此。在未来制备新型大并四苯的尝试中，应考虑AWA分子设计策略的局限性。
