High-potential perfluorinated phthalocyanine-fullerene dyads for generation of high-energy charge-separated states: formation and photoinduced electron-transfer studies.
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 (C60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine- (Py) and phenylimidazole-functionalised fullerene (C60Im) 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 substituents. 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 C60 entities, respectively; this suggests the formation of ZnF(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-C60Py(.-) (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C60 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 ZnF(n)Pc is higher than that of normal ZnPc-C60 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.
Department of Chemistry, University of North Texas, 1155 Union Circle, #305070, Denton, TX 76203-5017 (USA), Fax: (+1) 940-565-4318 francis.
Sushanta K
SK
Das
Andrew
A
Mahler
Angela K
AK
Wilson
Francis
F
D'Souza
D000838:Anions / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D002722:Chlorobenzenes / Q000737:chemistry; D004563:Electrochemistry / Q000379:methods; D004579:Electron Transport; D037741:Fullerenes / Q000737:chemistry*; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D007700:Kinetics; D008024:Ligands; D008027:Light; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D010777:Photochemistry / Q000379:methods; D011725:Pyridines / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods; D014050:Toluene / Q000737:chemistry; D015032:Zinc / Q000737:chemistry; D017967:Zinc Compounds
D000838:Anions; D002412:Cations; D002722:Chlorobenzenes; D037741:Fullerenes; D007211:Indoles; D054833:Isoindoles; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D017967:Zinc Compounds; C052159:Zn(II)-phthalocyanine; D014050:Toluene; C004726:2-dichlorobenzene; D015032:Zinc; C023666:pyridine; C013647:phthalocyanine
donor-acceptor systems; electron transfer; fullerenes; phthalocyanines; zinc