Schulze Erik J, Wu Mingjian, Hofmann Christina, Spiecker Erdmann, Hirsch Andreas
Department of Chemistry & Pharmacy, Chair of Organic Chemistry II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nikolaus-Fiebiger-Straße 10, 91058, Erlangen, Germany.
Institute of Micro- and Nanostructure Research (IMN), Center for Nanoanalysis and Electron Microscopy (CENEM) and Interdisciplinary Center for Nanostructured Films (IZNF), Friedrich-Alexander-Universität Erlangen-Nürnberg, Cauerstraße 3, 91058, Erlangen, Germany.
Chemistry. 2025 Aug 13;31(45):e02093. doi: 10.1002/chem.202502093. Epub 2025 Jul 22.
We report the synthesis of an amphiphilic tetra-porphyrin perylenebisimide (PBI) conjugate via four-fold Suzuki cross-coupling at the PBI ortho-position. Oligo-carboxylate Newkome-type G1 dendrons attached at the porphyrin periphery serve as polar head groups. Theoretical modelling corroborated the assumed planar discotic geometry. The amphiphile is very soluble in mixtures of basic water and THF, where it displays strong aggregation at high water content. Insights into the self-assembly process were obtained by tracking the individualization through THF addition using UV/Vis absorption spectroscopy. Here, a PBI-centred aggregation motif becomes evident. Further evaluation of the morphology via STEM and TEM imaging reveals that the assembly is guided by hydrophobic interactions as well as interactions of the carboxylates. These ortho-linked tetra-porphyrin PBI architectures fill a gap within the known families of porphyrin-PBI conjugates. Furthermore, the amphiphile is a valuable addition to the library of amphiphilic porphyrin-PBI conjugates, representing a discotic counterpart to the known calamitic architectures.
我们报道了通过在苝二酰亚胺（PBI）邻位进行四倍铃木交叉偶联合成两亲性四卟啉苝二酰亚胺（PBI）共轭物。连接在卟啉外围的低聚羧酸盐型纽科姆G1树枝状分子作为极性头基。理论建模证实了假定的平面盘状几何结构。该两亲物在碱性水和四氢呋喃（THF）的混合物中非常易溶，在高含水量时会表现出强烈的聚集。通过使用紫外/可见吸收光谱跟踪添加THF后的个体化过程，获得了对自组装过程的深入了解。在此，以PBI为中心的聚集模式变得明显。通过扫描透射电子显微镜（STEM）和透射电子显微镜（TEM）成像对形态进行的进一步评估表明，组装过程受疏水相互作用以及羧酸盐相互作用的引导。这些邻位连接的四卟啉PBI结构填补了已知卟啉-PBI共轭物家族中的一个空白。此外，该两亲物是两亲性卟啉-PBI共轭物库中的一个有价值的补充，代表了与已知棒状结构相对应的盘状结构。
