Synthesis of core-carbon substituted N-Confused porphyrin

研究了在氮杂卟啉（NCP）的内碳上引入卤素、金属等取代基的反应，发现当NBS存在时，NCP的内碳上发生了选择性溴代反应。该溴化NCP在吡啶中自发地转化为新的卟啉类化合物，其在1000 nm附近具有长波长吸收。用X-射线单晶衍射法对新化合物N-稠合卟啉（NEP）的结构进行了表征。NFP含有一个类似Hilstan的三环五环，它是由倒置的吡咯环的反转和与核心中相邻的吡咯环的氧化偶联而得到的。当NCP与Pd（II）或Ag（I）金属化后，得到了正方形平面四配位的NCP-金属配合物。通过磁化率测量、电化学研究和X射线结构分析，发现形成了抗磁性的Pd（II）或Ag（III）配合物。证明了NCP配体的多配价（-2和-3）

The introduction of substituents such as halogens and metals at the inner carbon of N-Confused porphyrin (NCP) was investigated.When NBS was used, selective bromination at the inner carbon of NCP was observed. This brominated NCP was spontaneously transformed into new porphyrinoid having a longwavelength absorption near 1000 nm while kept in pyridine. The structure of new compound, N-Fused Porphyrin (NEP), was characterized by x-ray single crystal diffraction. NFP contains a hilstan-like tricyclic penta ring, which derived from reinversion of inverted pyrrole ring and oxidative coupling to an adjacent pyrrole ring in the core. Furthermore, treatment of NFP with base gave starting NCP again.When NCP was metalated with Pd(II) or Ag(I), a square planar tetracoordinated NCP-metal complex was obtained. By magnetic susceptibility measurements, electrochemical study, and x-ray structural analyses, diamagnetic Pd(II) or Ag(III) complex was found formed. The multi ligand valence (-2 and -3) of NCP ligand was demonstrated