Kroonen Camiel C E, D'Addio Adriano, Prescimone Allesandro, Häussinger Daniel, Mayor Marcel
Department of Chemistry, University of Basel St Johanns-Ring 19 Basel 4056 Switzerland
Institute for Nanotechnology (INT), Karlsruhe Institute of Technology (KIT) P. O. Box 3640 Karlsruhe 76021 Germany.
Org Chem Front. 2024 Dec 4;12(5):1399-1408. doi: 10.1039/d4qo01808g. eCollection 2025 Feb 25.
This work explores the use of a cross-shaped organic framework that is used as a template for the investigation of multi-functionalized chromophores. We report the design and synthesis of a universal cross-shaped building block bearing two bromines and two iodines on its peripheral positions. The template can be synthesized on a gram scale in a five-step reaction comprising an oxidative homo-coupling macro-cyclization. The formed scaffold was selectively functionalized Suzuki cross-coupling reactions with methoxynaphthalene, naphthalimide and BODIPY derivatives, yielding a library of cross-shaped and chromophore-decorated model compounds, all of which were fully characterized. The formed racemic bis- and tetra-substituted crosses were resolved chiral stationary phase HPLC, and assignment of the enantiomers was done comparison of experimental and simulated electronic circular dichroism spectra as well as enantiomer single-crystal analysis. Additionally, the hybrid naphthalimide/BODIPY chromophore was found to be acting as an intramolecular Förster energy resonance transfer pair, which was investigated in more detail. With this easy-to-functionalize universal building block, we believe it might prove to be useful in the study of different sets of chromophores.
这项工作探索了一种十字形有机框架的用途，该框架被用作研究多功能发色团的模板。我们报告了一种通用十字形结构单元的设计与合成，其外围位置带有两个溴原子和两个碘原子。该模板可以通过包含氧化均相偶联大环化反应的五步反应以克级规模合成。通过与甲氧基萘、萘二甲酰亚胺和BODIPY衍生物的铃木交叉偶联反应，对所形成的支架进行选择性功能化，得到了一系列十字形且带有发色团修饰的模型化合物，所有这些化合物均得到了充分表征。通过手性固定相高效液相色谱法拆分了所形成的外消旋双取代和四取代十字形化合物，并通过比较实验和模拟的电子圆二色光谱以及对映体单晶分析完成了对映体的归属。此外，发现杂化萘二甲酰亚胺/BODIPY发色团可作为分子内福斯特能量共振转移对，并对此进行了更详细的研究。借助这种易于功能化的通用结构单元，我们相信它可能在不同发色团组的研究中证明是有用的。
