Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.
Chem Asian J. 2011 Feb 1;6(2):524-33. doi: 10.1002/asia.201000492. Epub 2010 Oct 4.
Zinc-porphyrin-appended norbornene derivative 6, the corresponding dimer 7, coherently aligned single-stranded polynorbornene 5, and zinc-porphyrin-linked double-stranded polymeric ladderphane 3 have been used for complexation with 1,4-diazabicyclo[2.2.2]octane (DABCO) to generate an array of porphyrin-DABCO supramolecular scaffolds. The stoichiometries of the complex formation are analyzed in detail by (1)H NMR spectroscopy as well as absorption and emission spectroscopic methods. Bidentate ligand DABCO is found to form with 7, 5, and 3 to give 2-to-1 porphyrin-DABCO sandwich structures. Monomer 6, on the other hand, forms a 2-to-1 porphyrin-DABCO sandwich structure at high concentration (20 mM), but a 1-to-1 porphyrin-DABCO complex at low concentration (10(-6) M). Time-resolved fluorescence decays revealed a similar behavior for the 2-to-1 porphyrin-DABCO sandwich structures that are formed from 3, 5, and 7.
锌卟啉修饰的降冰片烯衍生物 6、相应的二聚体 7、有序排列的单链聚降冰片烯 5 和锌卟啉连接的双链聚合梯形烷 3 已被用于与 1,4-二氮杂二环[2.2.2]辛烷（DABCO）络合，生成一系列卟啉-DABCO 超分子支架。通过（1）H NMR 光谱以及吸收和发射光谱方法详细分析了配合物形成的化学计量比。发现双齿配体 DABCO 与 7、5 和 3 形成 2:1 的卟啉-DABCO 夹心结构。另一方面，单体 6 在高浓度（20 mM）下形成 2:1 的卟啉-DABCO 夹心结构，但在低浓度（10(-6) M）下形成 1:1 的卟啉-DABCO 配合物。时间分辨荧光衰减表明，3、5 和 7 形成的 2:1 卟啉-DABCO 夹心结构具有相似的行为。
