Synthesis of core-carbon substituted N-Confused porphyrin

核碳取代的N-混淆卟啉的合成

• 批准号: 09640642
• 负责人: FURUTA Hiroyuki
• 金额: $ 1.92万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640642/
• 关键词: N-Confused Porphyrin; N-Fused Porphyrin; Silver(III) Complex; porphyrin isomer; 銀3価錯体; ニトロ化; 非線形光学材料

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

研究了在N-混淆卟啉(NCP)内部碳上引入卤素和金属等取代基的情况。当使用NBS时，观察到NCP内部碳上发生选择性溴化。当保留在吡啶中时，该溴化NCP自发转化为具有接近1000 nm的长波长吸收的新卟啉。新化合物N-稠合卟啉(NEP)的结构通过X射线单晶衍射进行了表征。 NFP含有类似hilstan的三环五环，其源自倒置吡咯环的再反转以及与核心中相邻吡咯环的氧化偶联。此外，用碱处理NFP再次得到起始NCP。当NCP用Pd(II)或Ag(I)金属化时，得到方形平面四配位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 Pd(II) 或 Ag(III) 络合物。证明了NCP配体的多配体价（-2和-3）

项目成果

Hiroyuki Furuta: "N-Fuseol Porphyrin from N-Confased Porphyrin" J.Am.Chem.Soc. 121(印刷中). (1999)

Hiroyuki Furuta：“来自 N-Confased 卟啉的 N-Fuseol 卟啉”J.Am.Chem.Soc. 121（出版中）。

Hiroyuki Furuta: "N-Confused Tetraphenyl porphyrin-Silver(VI)Complex" Inorg.Chem.38 印刷中. (1999)

Hiroyuki Furuta：“N-混乱的四苯基卟啉-银（VI）络合物”Inorg.Chem.38 正在印刷（1999）。

Hiroyuki Furuta: "N-Confused Tetraphenyloporphyrin-Silver(III)Complex" Inorg.Chem. 38(印刷中). (1999)

Hiroyuki Furuta：“N-混乱的四苯基卟啉-银（III）复合物”Inorg.Chem.38（印刷中）。

Hiroyuki Furuta: "N-Fused Porphyrin from N-Confused Porphyrin" J Am.Chem.Soc.121. 2945-2946 (1999)

Hiroyuki Furuta：“来自 N-混淆卟啉的 N-融合卟啉”J Am.Chem.Soc.121。

Hiroyuki Furuta, Takuji Ogawa, Yoshiya Uwatoko, Koichi Araki: "N-Confused Tetraphenylporphyrin-Silver(III) Complex" Inorg.Chem.(in press). (1999)

Hiroyuki Furuta、Takuji Okawa、Yoshiya Uwatoko、Koichi Araki：“N-混乱的四苯基卟啉-银（III）复合物”Inorg.Chem.（印刷中）。