Premium
Bismetal Complexes of 5,20‐Bis(5‐formyl‐2‐pyrrolyl)‐[26]hexaphyrin(1.1.1.1.1.1) Exhibiting Strong Near‐Infrared Region Absorptions
Author(s) -
Mori Hirotaka,
Osuka Atsuhiro
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500433
Subject(s) - chemistry , metalation , metal , lewis acids and bases , absorption (acoustics) , photochemistry , homo/lumo , infrared spectroscopy , ligand (biochemistry) , absorption spectroscopy , crystallography , stereochemistry , molecule , materials science , organic chemistry , catalysis , biochemistry , receptor , physics , quantum mechanics , composite material
[26]Hexaphyrin(1.1.1.1.1.1) bearing two 5‐formyl‐2‐pyrrolyl groups at the 5‐ and 20‐positions was prepared by cross‐condensation of 5,10‐bis(pentafluorophenyl)‐substituted tripyrrane with 2,5‐diformylpyrrole as an effective binuclear metal‐coordinating ligand, owing to the two hemiporphyrin‐like NNNN pockets. In fact, metalation of this hexaphyrin with Zn II , Cu II , and Pd II salts proceed smoothly at room temperature to give the corresponding bismetal complexes that displayed remarkably redshifted absorption spectra reaching deep into near infrared region. These redshifted absorption bands are ascribed, through electrochemical investigations and DFT calculations, to two structural motifs: the N ‐metalopyrrole substructure that elevates the HOMO level due to the electron‐donating property and the two coordinated metal ions that serve as Lewis acids to lower the LUMO level.