Premium
Mimicking Photosynthetic Antenna‐Reaction‐Center Complexes with a (Boron Dipyrromethene) 3 –Porphyrin–C 60 Pentad
Author(s) -
Liu JianYong,
ElKhouly Mohamed E.,
Fukuzumi Shunichi,
Ng Dennis K. P.
Publication year - 2011
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.201002333
Subject(s) - benzonitrile , photochemistry , chemistry , porphyrin , bathochromic shift , singlet state , moiety , ultrafast laser spectroscopy , bodipy , intramolecular force , cyclopentadienyl complex , triplet state , tetraphenylporphyrin , excited state , fluorescence , spectroscopy , stereochemistry , molecule , organic chemistry , catalysis , physics , quantum mechanics , nuclear physics
A highly efficient functional mimic of the photosynthetic antenna‐reaction‐center complexes has been designed and synthesized. The model contains a zinc(II) porphyrin (ZnP) core, which is connected to three boron dipyrromethene (BDP) units by click chemistry, and to a C 60 moiety using the Prato procedure. The compound has been characterized using various spectroscopic methods. The intramolecular photoinduced processes of this pentad have also been studied in detail with steady‐state and time‐resolved absorption and emission spectroscopic methods, both in polar benzonitrile and nonpolar toluene. The BDP units serve as the antennae, which upon excitation undergo singlet–singlet energy transfer to the porphyrin core. This is then followed by an efficient electron transfer to the C 60 moiety, resulting in the formation of the singlet charge‐separated state (BDP) 3 –ZnP . + –C 60 . − , which has a lifetime of 476 and 1000 ps in benzonitrile and toluene, respectively. Interestingly, a slow charge‐recombination process ( ${k{{{\rm T}\hfill \atop {\rm CR}\hfill}}}$ =2.6×10 6 s −1 ) and a long‐lived triplet charge‐separated state ( ${\tau {{{\rm T}\hfill \atop {\rm CS}\hfill}}}$ =385 ns) were detected in polar benzonitrile by nanosecond transient measurements.