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Synthesis and properties of a meso- tris–ferrocene appended zinc(II) porphyrin and a critical evaluation of its dye sensitised solar cell (DSSC) performance

Lookup NU author(s): Dr Dumitru Sirbu, Professor Constantin Turta, Professor Andrew Benniston, Professor Elizabeth GibsonORCiD



This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0).


A zinc(II) porphyrin derivative, F3P, was prepared containing a single ferrocene group appended at three of the meso positions. The final meso position contains a benzoic acid unit, and was designed to be an anchoring moiety to a semiconductor surface. The cyclic voltammogram for the porphyrin derivative reveals that the three ferrocene units are oxidised and reduced at E-1/2 = + 0.04 V vs. Fc+/Fc. Other redox responses are porphyrin- based at + 1.1 V vs. Fc+/Fc (irreversible) and -1.87 V and -2.20 V vs. Fc+/Fc (both quasi-reversible). The room temperature M "ossbauer spectrum for F3P comprises a doublet (delta Fe 0.44 mm s(-1); Delta E-Q 2.35 mm s(-1); peak width 0.27 mm s(-1)). The data are consistent with the ferrocene groups non- interacting with the porphyrin moiety in the ground state. Excitation of the compound in THF with an ultra-short laser pulse produces in less than 1 ps the charge separated state which comprises Fc(+center dot) -porp(-center dot) and decays back to the ground state in 24 ps. Roughly the same behaviour is observed for the dye absorbed on TiO2, the only slight difference is the appearance of a long-lived component in the decay records. The electron for the porphyrin radical anion does not inject into the conduction band of the TiO2, only the porphyrin excited state participates in any electron injection process. Partly because of this factor the performance of the dye attached to TiO2 in a DSSC device is rather limited (J(SC) = 0.068 mA cm(-2), V-OC = 283 mV, FF = 0.42, eta = 0.008%).

Publication metadata

Author(s): Sirbu D, Turta C, Benniston AC, Lemmetyinen H, Tkachenko NV, Wood C, Gibson E

Publication type: Article

Publication status: Published

Journal: RSC Advances

Year: 2014

Volume: 4

Issue: 43

Pages: 22733-22742

Online publication date: 13/05/2014

Acceptance date: 12/05/2014

Date deposited: 24/07/2014

ISSN (electronic): 2046-2069

Publisher: RSC Publications


DOI: 10.1039/C4RA03105A


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Funder referenceFunder name
Nottingham University
Newcastle University
246902FP7-PEOPLE-2009-IRSES grant
263486Academy of Finland grant