Issue 33, 2018

Interfacing tetrapyridyl-C60 with porphyrin dimers via π-conjugated bridges: artificial photosynthetic systems with ultrafast charge separation

Abstract

We report on the synthesis, characterization and photophysical properties of a donor–bridge–acceptor supramolecular hybrid system, consisting of a tetrapyridyl fullerene derivative (C60-tpyr) as electron acceptor, with the four pyridyl groups as part of oligophenyleneethynylene/phenylenevinylene bridges, and zinc porphyrin dimers (ZnP)2 as electron donor species. Based on the metal-to-ligand coordination between the zinc metal centers of (ZnP)2 and the four pyridyl entities of C60-tpyr, a strong binding constant (5 × 105 M−1) for the formation of C60-tpyr·[(ZnP)2]2 was evidenced. Insights into the electronic interactions between the photoactive (ZnP)2 units and C60-tpyr emanated from complementary physicochemical assays, which were further supported by theoretical calculations. Notably, the absorption and emission titration assays revealed strong interactions between the electron donor and acceptor species within C60-tpyr·[(ZnP)2]2, both in the ground and excited state. Moreover, femtosecond and nanosecond laser photolysis transient absorption measurements were performed and provided solid evidence for intramolecular electron transfer processes derived from the singlet excited state of (ZnP)2 to C60-tpyr. Comparison with systems in which either four monomeric zinc porphyrins (ZnP) were complexed with C60-tpyr or a (ZnP)2 was coordinated with a dipyridylfullerene revealed the beneficial role of C60-tpyr in increasing the lifetime of charge-separation.

Graphical abstract: Interfacing tetrapyridyl-C60 with porphyrin dimers via π-conjugated bridges: artificial photosynthetic systems with ultrafast charge separation

Supplementary files

Article information

Article type
Paper
Submitted
18 May 2018
Accepted
12 Jul 2018
First published
12 Jul 2018

Phys. Chem. Chem. Phys., 2018,20, 21269-21279

Interfacing tetrapyridyl-C60 with porphyrin dimers via π-conjugated bridges: artificial photosynthetic systems with ultrafast charge separation

C. Stangel, F. Plass, A. Charisiadis, E. Giannoudis, G. Chararalambidis, K. Karikis, G. Rotas, G. E. Zervaki, N. N. Lathiotakis, N. Tagmatarchis, A. Kahnt and A. G. Coutsolelos, Phys. Chem. Chem. Phys., 2018, 20, 21269 DOI: 10.1039/C8CP03172J

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