Pictet‐Spengler Synthesis of Fused‐Azepine‐ and 1 H ‐Azocine‐Bridged Ni II Porphyrin Dimers

Angewandte Chemie International Edition 2026

View at publisher
Authors: Yuanyuan Li, Xiaojie Liu, H. Alexander Chen, Mingbo Zhou, Ling Xu, Yutao Rao, Bangshao Yin, Tomohiro Higashino, Atsuhiro Osuka, Jianxin Song
DOI: 10.1002/anie.7602426
Cited by: 2
References: 77

Abstract

ABSTRACT Pictet‐Spengler cyclization of meso‐amino and meso, meso ’‐diamino β‐β '‐linked Ni II porphyrin dimers 1Ni and 2Ni with paraformaldehyde gave fused azepine‐bridged Ni II porphyrin dimers 3Ni and 4Ni , respectively. Oxidation of 3Ni with FeCl3 and 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) provided additionally meso ‐ tert buylphenyl‐fused dimer 5Ni in 43% yield but the similar oxidation of 4Ni led to the formation of singly meso ‐ tert buylphenyl‐fused dimer 6Ni in 94% yield. Fused 1 H ‐azocine‐bridged Ni II porphyrin dimer 8Ni was synthesized by the similar Pictet‐Spengler cyclization of meso ‐amino β ‐meso’ linked Ni II porphyrin dimer 7Ni . 3Ni and 4Ni were converted to the corresponding free bases and Zn II complexes, which display fairly red‐shifted absorption bands and fluorescence in the near infrared (NIR) region.

Fields of Study & Subjects

Porphyrin and Phthalocyanine Chemistry Coordination Chemistry and Organometallics Organometallic Complex Synthesis and Catalysis

Publication details

Journal / source
Angewandte Chemie International Edition
Publisher
Wiley
Volume
65
Issue
15
Pages
e7602426–e7602426
Publication date
25 February 2026
Language
EN