Institut de Chimie Moléculaire de l'Université de Bourgogne, UMR CNRS 6302, Université de Bourgogne, BP 47870, 21078 Dijon Cedex, France.
Dalton Trans. 2013 Jan 28;42(4):1196-209. doi: 10.1039/c2dt31667f.
The effects of a direct connection between ferrocene and porphyrin units have been thoroughly investigated by electrochemical and spectroscopic methods. These data not only reveal that substitution of the porphyrin macrocycle by one, two, three or four ferrocenyl groups strongly affects the electronic properties of the porphyrin and ferrocenyl moieties, they also clearly demonstrate that the metallocene centres are "connected" through the porphyrin-based electronic network. The dynamic properties of selected ferrocene-porphyrin conjugates have been investigated by VT NMR and metadynamic calculations. 1,3-Dithiolanyl protecting groups have been introduced on the upper rings of the ferrocene fragments to allow a straightforward and easy access to redox active picket-fence porphyrins. X-ray diffraction analyses of the zinc(II) 5-[1'-[2-(1,3-dithiolanyl)]ferrocenyl]-10,15,20-tri(p-tolyl)porphyrin and 5,15-bis[1'-[2-(1,3-dithiolanyl)]ferrocenyl]-10,20-bis(p-tolyl)porphyrin complexes reveal the existence of S-Zn bonds involved in supramolecular arrays. The solid state analysis of the trans-5,15-di-(1'-(formyl)ferrocenyl)-10,20-di-(p-tolyl)-porphyrinatozinc(II) complex, obtained by deprotection of the dithiolane substituted analog, is conversely found in the crystal lattice as a monomer exhibiting a hexacoordinated zinc metal centre.
电化学和光谱方法彻底研究了二茂铁和卟啉单元之间的直接连接的影响。这些数据不仅表明卟啉大环被一个、两个、三个或四个二茂铁基取代强烈影响卟啉和二茂铁部分的电子性质，而且还清楚地表明金属中心通过基于卟啉的电子网络“连接”。通过 VT NMR 和元动力学计算研究了选定的二茂铁-卟啉缀合物的动态性质。在二茂铁片段的上环上引入了 1,3-二硫醇基保护基团，以允许直接且容易地获得氧化还原活性的尖桩篱笆卟啉。锌（II）5-[1'-[2-（1,3-二硫醇基）]二茂铁基]-10,15,20-三（对甲苯基）卟啉和 5,15-双[1'-[2-（1,3-二硫醇基）]二茂铁基]-10,20-双（对甲苯基）卟啉配合物的 X 射线衍射分析表明存在涉及超分子排列的 S-Zn 键。通过保护的二硫代烷取代类似物的去保护获得的反式 5,15-二-（1'-(甲酰基)二茂铁基）-10,20-二-（对甲苯基）-卟啉酸锌（II）配合物的固态分析相反地被发现作为单体存在于晶格中，其具有六配位的锌金属中心。
