Journal
CHEMPHYSCHEM
Volume 15, Issue 12, Pages 2462-2472Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201402118
Keywords
donor-acceptor systems; electron transfer; fullerenes; phthalocyanines; zinc
Funding
- National Science Foundation [1110942]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1110942] Funding Source: National Science Foundation
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High oxidation potential perfluorinated zinc phthalocyanines (ZnF(n)Pcs) are synthesised and their spectroscopic, redox, and light-induced electron-transfer properties investigated systematically by forming donor-acceptor dyads through metal-ligand axial coordination of fullerene (C-60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine-(Py) and phenylimidazole-functionalised fullerene (C(60)Im) derivatives to the zinc centre of the F(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) M-1; nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine sub-stituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6-31G* method. The HOMO and LUMO levels are located on the Pc and C-60 entities, respectively; this suggests the formation of ZnFnPcC center dot+-C(60)Im(center dot-) and ZnFnPcC center dot+-C60PyC center dot- (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C-60 dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge-separated states. The energy of the charge-separated state for dyads composed of ZnFnPc is higher than that of normal ZnPc-C-60 dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar-energy harvesting and optoelectronic device building applications.
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