Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Kemigården 4, 412 96 Gothenburg, Sweden.
Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials (ICMM) Chair of Organic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany.
J Am Chem Soc. 2022 May 25;144(20):8977-8986. doi: 10.1021/jacs.2c00456. Epub 2022 May 11.
Inspired by light-induced processes in nature to mimic the primary events in the photosynthetic reaction centers, novel functional materials combine electron donors and acceptors, i.e., (metallo)porphyrins (ZnP) and fullerenes (C), respectively, with emerging materials, i.e., nanographenes. We utilized hexa--hexabenzocoronene (HBC) due to its versatility regarding functionalization and physicochemical properties, to construct three regioisomeric ZnP-HBC-C conjugates, which foster geometrical diversity by arranging ZnP and C in -, -, and -positions to each other. The corresponding hexaarylbenzene (HAB) motifs, with an interrupted π-system, were also prepared. Transient absorption measurements disclosed the fast population of charge transfer as well as singlet and triplet charge-separated states. With the help of density functional theory (DFT) calculations, we further conceive the communication across the HBCs and HABs. This work reveals the impact of both the geometrical arrangement with respect to through-space versus through-bond interactions and the structural rigidity/flexibility on the charge management across the different π-systems.
受自然界中光诱导过程的启发，为了模拟光合作用反应中心的初始事件，新型功能材料将电子供体和受体（即（金属）卟啉（ZnP）和富勒烯（C））与新兴材料（即纳米石墨烯）结合在一起。我们利用具有多功能官能化和物理化学性质的六--六苯并冠烯（HBC），构建了三种区域异构体的 ZnP-HBC-C 缀合物，通过将 ZnP 和 C 彼此以 - 、 - 和 - 位排列来促进几何多样性。还制备了具有中断的π-体系的相应六芳基苯（HAB）基序。瞬态吸收测量揭示了电荷转移以及单重态和三重态电荷分离态的快速形成。借助密度泛函理论（DFT）计算，我们进一步设想了 HBC 和 HAB 之间的通信。这项工作揭示了几何排列相对于隔空与成键相互作用以及结构刚性/柔性对不同π-体系之间电荷管理的影响。
