Department of Chemistry, University of Wrocław ul. F.Joliot-Curie 14, 50-383 Wrocław, Poland.
Chemistry. 2011 Mar 14;17(12):3500-11. doi: 10.1002/chem.201002765. Epub 2011 Feb 22.
An annulene-porphyrin hybrid, the diaaza-deficient porphyrin 5,10,15,20-tetraaryl-21,23-divacataporphyrin, has been synthesized by an extrusion of tellurium atom(s) from 5,10,15,20-tetraaryl-21,23-ditelluraporphyrin under treatment with HCl. In addition, a monoaza-deficient 5,10,15,20-tetraaryl-21-tellura-23-vacataporphyrin was formed in the same reaction. The two new members of the vacataporphyrin family were characterized by X-ray crystallography, as well as UV/Vis and NMR spectroscopy. These aromatic molecules preserve the fundamental structural and spectroscopic features of the parent tetraarylporphyrin. The X-ray crystal structures of 21,23-divacataporphyrin and 21-tellura-23-vacataporphyrin show typical porphyrin patterns. The molecules are not strictly planar and show distortion of the annulene moieties. The N22⋅⋅⋅N24 distances (5.23 and 5.09 Å) are considerably longer than in regular porphyrins. For 21,23-divacataporphyrin, variable-temperature (1)H NMR spectroscopy data allowed the identification of divacataporphyrin stereoisomers differentiated by the geometry of the butadiene bridges. The forms remain in thermodynamic equilibrium.
一个薁并卟啉杂化物，即通过用 HCl 处理从 5,10,15,20-四芳基-21,23-二碲代卟啉中挤出一个或多个碲原子得到的缺氮卟啉 5,10,15,20-四芳基-21,23-二脱氮薁并卟啉，以及一个单氮缺的 5,10,15,20-四芳基-21-碲代-23-脱氮薁并卟啉，在相同的反应中形成。这两个新的脱氮薁并卟啉家族成员通过 X 射线晶体学、紫外/可见光谱和 NMR 光谱进行了表征。这些芳香族分子保留了母体四芳基卟啉的基本结构和光谱特征。21,23-二脱氮薁并卟啉和 21-碲代-23-脱氮薁并卟啉的 X 射线晶体结构显示出典型的卟啉模式。分子不是严格平面的，并且显示出薁环部分的变形。N22⋅⋅⋅N24 距离（5.23 和 5.09 Å）比常规卟啉长得多。对于 21,23-二脱氮薁并卟啉，变温（1）H NMR 光谱数据允许鉴定通过丁二烯桥的几何形状区分的二脱氮薁并卟啉立体异构体。这些形式保持热力学平衡。
