Synthesis of core-carbon substituted N-Confused porphyrin

研究了N-混杂卟啉(NCP)内碳引入卤素和金属等取代基时，NCP内碳发生选择性溴化反应。这种溴化的NCP在吡啶中保存时，自发转化为新的卟啉类化合物，在1000 nm附近有长波吸收。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含有一个炮形的三环五环，它来自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。当NCP与Pd(II)或Ag(I)金属化时，得到了四配位的四配位NCP-金属络合物。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)络合物。证明了NCP配体的多配位价(-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