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A Light‐Harvesting/Charge‐Separation Model with Energy Gradient Made of Assemblies of meta ‐Pyridyl Zinc Porphyrins
Author(s) -
Otsuki Joe,
Okumura Takumi,
Sugawa Kosuke,
Kawano Shinichiro,
Tanaka Kentaro,
Hirao Takehiro,
Haino Takeharu,
Lee Yu Jin,
Kang Seongsoo,
Kim Dongho
Publication year - 2021
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.202003327
Subject(s) - porphyrin , chemistry , supramolecular chemistry , trimer , ferrocene , moiety , vapor pressure osmometry , proton nmr , nuclear magnetic resonance spectroscopy , zinc , photochemistry , molecule , organic chemistry , dimer , vapor pressure , electrode , electrochemistry
Self‐assembly of porphyrins is a fascinating topic, not only for mimicking chlorophyll assemblies in photosynthetic organisms, but also for the potential of creating molecular‐level devices. Herein, zinc porphyrin derivatives bearing a meta ‐pyridyl group at the meso position were prepared and their assemblies studied in chloroform. Among the porphyrins studied, one with a carbamoylpyridyl moiety gave a distinct 1 H NMR spectrum in CDCl 3 , which allowed the supramolecular structure in solution to be probed in detail. Ring‐current‐induced chemical‐shift changes in the 1 H NMR spectrum, together with vapor‐pressure osmometry and diffusion‐ordered NMR spectroscopy, among other evidence, suggested that the porphyrin molecules form a trimer with a triangular cone structure. Incorporation of a directly linked porphyrin–ferrocene dyad with the same assembling properties in the assemblies led to a rare example of a light‐harvesting/charge‐separation system in which an energy gradient is incorporated and reductive quenching occurs.