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D 3 h ‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity
Author(s) -
Ohkoda Yohei,
Asaishi Akane,
Namiki Tomoya,
Hashimoto Tomoaki,
Yamada Midori,
Shirai Koichiro,
Katagami Yuta,
Sugaya Tomoaki,
Tadokoro Makoto,
Satake Akiharu
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.201501854
Subject(s) - trimer , porphyrin , chemistry , crystallography , palladium , nuclear magnetic resonance spectroscopy , stereochemistry , ring (chemistry) , tetramer , denticity , polymer chemistry , dimer , crystal structure , photochemistry , organic chemistry , catalysis , enzyme
The one‐step synthesis of D 3 h ‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso ‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η 3 ‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η 3 ‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.