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Cyclic Tetramers of Zinc Chlorophylls as a Coupled Light‐Harvesting Antenna–Charge‐Separation System
Author(s) -
Shinozaki Yoshinao,
Ohkubo Kei,
Fukuzumi Shunichi,
Sugawa Kosuke,
Otsuki Joe
Publication year - 2016
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.201503789
Subject(s) - photochemistry , chemistry , tetramer , fullerene , singlet state , zinc , acceptor , photoinduced charge separation , p700 , ultrafast laser spectroscopy , materials science , spectroscopy , excited state , photosystem i , atomic physics , organic chemistry , photosystem ii , photosynthesis , artificial photosynthesis , physics , photocatalysis , quantum mechanics , enzyme , condensed matter physics , catalysis , biochemistry
A coupled light‐harvesting antenna–charge‐separation system, consisting of self‐assembled zinc chlorophyll derivatives that incorporate an electron‐accepting unit, is reported. The cyclic tetramers that incorporated an electron acceptor were constructed by the co‐assembly of a pyridine‐appended zinc chlorophyll derivative, ZnPy , and a zinc chlorophyll derivative further decorated with a fullerene unit, ZnPyC 60 . Comprehensive steady‐state and time‐resolved spectroscopic studies were conducted for the individual tetramers of ZnPy and ZnPyC 60 as well as their co‐tetramers. Intra‐assembly singlet energy transfer was confirmed by singlet–singlet annihilation in the ZnPy tetramer. Electron transfer from the singlet chlorin unit to the fullerene unit was clearly demonstrated by the transient absorption of the fullerene radical anion in the ZnPyC 60 tetramer. Finally, with the co‐tetramer, a coupled light‐harvesting and charge‐separation system with practically 100 % quantum efficiency was demonstrated.