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Novel Iron-Based Polynuclear Metal Complexes [FeII(L)(CN)4]2–[FeIII(H2O)3Cl]2: Synthesis and Study of Photovoltaic Properties for Dye-Sensitized Solar Cell

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Abstract

A series of novel polynuclear iron-based photosensitizers (1–3) with cyano-bridged to form a molecular square were synthesized and their optical, electrochemical, and photovoltaic properties were investigated. The modification of anchoring groups with 4,4'-dicarboxy-2,2'-bipyridine, 2,2'-bipyridine, and 4,4'-dimethoxy-2,2'-bipyridine does not show significant changes on the both absorption and electrochemical properties of these iron-based dyes. This indicates that the polynuclear iron-based photosensitizers have better flexibility to regulate their physical properties of solubility, surface absorption, and thin-film formation for device preparation. The polynuclear new dyes show power conversion efficiencies ranged from 0.43 to 0.48% that is almost the best system among the published iron-based photosensitizers. These iron-based dyes were able to chemisorb on TiO2 surface efficiently and then promoting electron injection and photocurrent generation in a dye-sensitized solar cell with solar irradiation.

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References

  1. Balasingam, S.K., Lee, M., Kang, M.G., and Jun, Y., Improvement of dye-sensitized solar cells toward the broader light harvesting of the solar spectrum, Chem. Commun., 2013, vol. 49, p. 1471.

    Article  CAS  Google Scholar 

  2. Du, Z., Zhang, H., Bao, H., and Zhong, X., Optimization of TiO2 photoanode films for highly efficient quantum dot-sensitized solar cells, J. Mater. Chem. A, 2014, vol. 2, p. 13033.

    Article  CAS  Google Scholar 

  3. Lu, X., Lan, T., Qin, Z., Wang, Z.S., and Zhou, G., A near-infrared dithieno[2,3-a:3',2'-c]phenazinebased organic co-sensitizer for highly efficient and stable quasi-solid-state dye-sensitized solar cells, ACS Appl. Mater. Interfaces, 2014, vol. 6, p. 19308.

    Article  CAS  PubMed  Google Scholar 

  4. Mai, C.L., Moehl, T., Hsieh, C.H., Decoppet, J.D., Zakeeruddin, S.M., Grätzel, M., and Yeh, C.Y., Porphyrin sensitizers bearing a pyridine-type anchoring group for dye-sensitized solar cells, ACS Appl. Mater. Interfaces, 2015, vol. 7, p. 14975.

    Article  CAS  PubMed  Google Scholar 

  5. O’Regan, M.G.B., A low-cost, high-effeciency solar cell based on dye-sensitized colloidal TiO2 films, Nature, 1991, vol. 353, p. 737.

    Article  Google Scholar 

  6. Wu, Y., Zhu, W.H., Zakeeruddin, S.M., and Grätzel, M., Insight into D-A-pi-A structured sensitizers: a promising route to highly efficient and stable dye-sensitized solar cells, ACS Appl. Mater. Interfaces, 2015, vol. 7, p. 9307.

    Article  CAS  PubMed  Google Scholar 

  7. Park, H.J., Kim, K.H., Choi, S.Y., Kim, H.M., Lee, W.I., Kang, Y.K., and Chung, Y.K., Unsymmetric Ru(II) complexes with N-heterocyclic carbene and/or terpyridine ligands: synthesis, characterization, ground-and excited-state electronic structures and their application for DSSC sensitizers, Inorg. Chem., 2010, vol. 49, p. 7340.

    Article  CAS  PubMed  Google Scholar 

  8. Fredin, L.A., Papai, M., Rozsalyi, E., Vanko, G., Warnmark, K., Sundstrom, V., and Persson, P., Exceptional excited-state lifetime of an iron(II)-N-heterocyclic carbene complex explained, J. Phys. Chem. Lett., 2014, vol. 5, p. 2066.

    Article  CAS  PubMed  Google Scholar 

  9. Monari, A., Assfeld, X., Beley, M., and Gros, P.C., Theoretical study of new ruthenium-based dyes for dye-sensitized solar cells, J. Phys. Chem. A, 2011, vol. 115, p. 3596.

    Article  CAS  PubMed  Google Scholar 

  10. Etienne, T., Assfeld, X., and Monari, A., Toward a quantitative assessment of electronic transitions’ charge-transfer character, J. Chem. Theory Comp., 2014, vol. 10, p. 3896.

    Article  CAS  Google Scholar 

  11. Juban, E.A., Smeigh, A.L., Monat, J.E., and McCusker, J.K., Ultrafast dynamics of ligand-field excited states, Coordin. Chem. Rev., 2006, vol. 250, p. 1783.

    Article  CAS  Google Scholar 

  12. Cannizzo, A., Milne, C.J., Consani, C., Gawelda, W., Bressler, C., van Mourik, F., and Chergui, M., Lightinduced spin crossover in Fe(II)-based complexes: the full photocycle unraveled by ultrafast optical and X-ray spectroscopies, Coordin. Chem. Rev., 2010, vol. 254, p. 2677.

    Article  CAS  Google Scholar 

  13. Sano, Y., Onoda, A., and Hayashi, T., A hydrogenase model system based on the sequence of cytochrome c: photochemical hydrogen evolution in aqueous media, Chem. Commun., 2011, vol. 47, p. 8229.

    Article  CAS  Google Scholar 

  14. Jamula, L.L., Brown, A.M., Guo, D., and McCusker, J.K., Synthesis and characterization of a high-symmetry ferrous polypyridyl complex: approaching the 5T2/3T1 crossing point for Fe(II), Inorg. Chem., 2014, vol. 53, p. 15.

    Article  CAS  PubMed  Google Scholar 

  15. Li, L.L. and Diau, E.W., Porphyrin-sensitized solar cells, Chem. Soc. Rev., 2013, vol. 42, p. 291.

    Article  CAS  PubMed  Google Scholar 

  16. Bowman, D.N., Blew, J.H., Tsuchiya, T., and Jakubikova, E., Elucidating band-selective sensitization in iron(II) polypyridine-TiO2 assemblies, E., Inorg. Chem., 2013, vol. 52, p. 8621.

    Article  CAS  Google Scholar 

  17. Xia, H.L., Ardo, S., Sarjeant, A.A.N., Huang, S., and Meyer, G.J., Photodriven spin change of Fe(II) benzimidazole compounds anchored to nanocrystalline TiO2 thin films, Langmuir, 2009, vol. 25, p. 13641.

    Article  CAS  PubMed  Google Scholar 

  18. Mukherjee, S., Bowman, D.N., and Jakubikova, E., Cyclometalated Fe(II) complexes as sensitizers in dyesensitized solar cells, E., Inorg. Chem., 2015, vol. 54, p. 560.

    Article  CAS  Google Scholar 

  19. Liu, Y., Harlang, T., Canton, S.E., Chabera, P., Suarez-Alcantara, K., Fleckhaus, A., Vithanage, D.A., Goransson, E., Corani, A., Lomoth, R., Sundstrom, V., and Warnmark, K., Towards longer-lived metal-toligand charge transfer states of iron(II) complexes: an N-heterocyclic carbene approach, Chem. Commun., 2013, vol. 36, p. 6412.

    Article  CAS  Google Scholar 

  20. Duchanois, T., Etienne, T., Cebrián, C., Liu, L., Monari, A., Beley, M., Assfeld, X., Haacke, S., and Gros, P.C., An iron-based photosensitizer with extended excited-state lifetime: photophysical and photovoltaic properties, Eur. J. Inorg. Chem., 2015, vol. 2015, p. 2469.

    Article  CAS  Google Scholar 

  21. Bowman, D.N., Mukherjee, S., Barnes, L.J., and Jakubikova, E., Linker dependence of interfacial electron transfer rates in Fe(II)-polypyridine sensitized solar cells, J. Phys. Condens. Mat., 2015, vol. 27, p. 134.

    Article  CAS  Google Scholar 

  22. Wu, W., Sun, J., Ji, S., Wu, W., Zhao, J., and Guo, H., Tuning the emissive triplet excited states of platinum( II) Schiff base complexes with pyrene, and application for luminescent oxygen sensing and triplet-triplet-annihilation based upconversions, Dalton Trans., 2011, vol. 40, p. 11550.

    Article  CAS  PubMed  Google Scholar 

  23. Dixon, I.M., Khan, S., Alary, F., Boggio-Pasqua, M., and Heully, J.L., Probing the photophysical capability of mono and bis(cyclometallated) Fe(II) polypyridine complexes using inexpensive ground state DFT, Dalton Trans., 2014, vol. 43, p. 15898.

    Article  CAS  PubMed  Google Scholar 

  24. Canton, S.E., Zhang, X., Daku, M.L.L., Liu, Y., Zhang, J., and Alvarez, S., Mapping the ultrafast changes of continuous shape measures in photoexcited spin crossover complexes without long-range order, J. Phys. Chem. C, 2015, vol. 119, p. 3322.

    Article  CAS  Google Scholar 

  25. Sun, Q., Mosquera-Vazquez, S., Daku, L.M.L., Guénée, L., Goodwin, H.A., Vauthey, E., and Hauser, A., Experimental evidence of ultrafast quenching of the 3MLCT luminescence in ruthenium(II) tris-bipyridyl complexes via a 3dd state, J. Am. Chem. Soc., 2013, vol. 135, p. 13660.

    Article  CAS  PubMed  Google Scholar 

  26. Liu, Y., Kjaer, K.S., Fredin, L.A., Chabera, P., Harlang, T., Canton, S.E., Lidin, S., Zhang, J., Lomoth, R., Bergquist, K.E., Persson, P., Warnmark, K., and Sundstrom, V., A heteroleptic ferrous complex with mesoionic bis(1,2,3-triazol-5-ylidene) ligands: taming the MLCT excited state of iron(II), Chem. Eur. J., 2015, vol. 21, p. 3628.

    Article  CAS  PubMed  Google Scholar 

  27. Dixon, I.M., Alary, F., Boggio-Pasqua, M., and Heully, J.L., The (N4C2)2-donor set as promising motif for bis(tridentate) iron(II) photoactive compounds, Inorg. Chem., 2013, vol. 52, p. 13369.

    Article  CAS  PubMed  Google Scholar 

  28. Szaciłowski, K., Chmura, A., and Stasicka, Z., Interplay between iron complexes, nitric oxide and sulfur ligands: structure, (photo)reactivity and biological importance, Coordin. Chem. Rev., 2005, vol. 249, p. 2408.

    Article  CAS  Google Scholar 

  29. Bowman, D.N. and Jakubikova, E., Low-spin versus high-spin ground state in pseudo-octahedral iron complexes, Inorg. Chem., 2012, vol. 51, p. 6011.

    Article  CAS  PubMed  Google Scholar 

  30. Brown, A.M., McCusker, C.E., and McCusker, J.K., Spectroelectrochemical identification of charge-transfer excited states in transition metal-based polypyridyl complexes, Dalton. Trans., 2014, vol. 43, p. 17635.

    Article  CAS  PubMed  Google Scholar 

  31. Tobias, Y.L., Harlang, C.B., and Gordivska, O., Iron sensitizer converts light to electrons with 92% yeild, Nature Chem., 2015, vol. 7, p. 883.

    Article  CAS  Google Scholar 

  32. Das, A.K., Solomon, R.V., Hofmann, F., and Meuwly, M., Inner-shell water rearrangement following photoexcitation of tris(2,2'-bipyridine)iron(II), J. Phys. Chem. B, 2016, vol. 120, p. 206.

    Article  CAS  PubMed  Google Scholar 

  33. Newton, G.N., Nihei, M., and Oshio, H., Cyanidebridged molecular squares–the building units of Prussian blue, Eur. J. Inorg. Chem., 2011, vol. 20, p. 3031.

    Article  CAS  Google Scholar 

  34. Li, F., Clegg, J.K., Goux-Capes, L., Chastanet, G., D’Alessandro, D.M., Létard, J.F., and Kepert, C.J., A mixed-spin molecular square with a hybrid [2×2]grid/metallocyclic architecture, Angew. Chem. Int. Ed., 2011, vol. 50, p. 2820.

    Article  CAS  Google Scholar 

  35. Wu, D., Zhang, Y., Huang, W., and Sato, O., An S = 3 cyanide-bridged tetranuclear FeIII2NiII2 square that exhibits slow relaxation of magnetization: synthesis, structure and magnetic properties, Dalton Trans., 2010, vol. 39, p. 5500.

    Article  CAS  PubMed  Google Scholar 

  36. Peng, Y.H., Meng, Y.F., Hu, L., Li, Q.X., Li, Y.Z., Zuo, J.L., and You, X.Z., Syntheses, structures, and magnetic properties of heterobimetallic clusters with tricyanometalate and pi-conjugated ligands containing 1,3-dithiol-2-ylidene, Inorg. Chem., 2010, vol. 49, p. 1905.

    Article  CAS  PubMed  Google Scholar 

  37. Etienne, T., Assfeld, X., and Monari, A., New insight into the topology of excited states through detachment/ attachment density matrices-based centroids of charge, J. Chem. Theory Comp., 2014, vol. 10, p. 3906.

    Article  CAS  Google Scholar 

  38. Duchanoi, S.T., Etienne, T., Beley, M., Assfeld, X., Perpète, E.A., Monari, A., and Gros, P.C., Heteroleptic pyridyl-carbene iron complexes with tuneable electronic properties, Eur. J. Inorg. Chem., 2014, vol. 23, p. 3747.

    Article  CAS  Google Scholar 

  39. Monari, A., Very, T., Rivail, J.L., and Assfeld, X., A QM/MM study on the spinach plastocyanin: redox properties and absorption spectra, Comp. Theor. Chem., 2012, vol. 990, p. 119.

    Article  CAS  Google Scholar 

  40. Dell’Orto, E., Raimondo, L., Sassella, A., and Abbotto, A., Dye-sensitized solar cells: spectroscopic evaluation of dye loading on TiO2, J. Mater. Chem., 2012, vol. 22, p. 11364.

    Article  CAS  Google Scholar 

  41. Briand, J., Bräm, O., Réhault, J., Léonard, J., Cannizzo, A., Chergui, M., Zanirato, V., Olivucci, M., Helbing, J., and Haacke, S., Coherent ultrafast torsional motion and isomerization of a biomimetic dipolar photoswitch, Phys. Chem. Chem. Phys., 2010, vol. 12, p. 3178.

    Article  CAS  PubMed  Google Scholar 

  42. Ren, X.M., Feng, Q.Y., Zhou, G., Huang, C.H., and Wang, Z.S., Effect of cations in coadsorbate on charge recombination and conduction band edge movement in dye-sensitized solar sells, J. Phys. Chem. C, 2010, vol. 114, p. 7190.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Key Laboratory of Analytical Chemistry of the State Ethnic Affairs Commission, College of Chemistry and Materials Science, South-Central University for Nationalities, Wuhan, 430074, China

    Jue Wang & Chunya Li

  2. Department of Science and Environmental Studies, Centre for Education in Environmental Sustainability, The Education University of Hong Kong, Tai Po, Hong Kong SAR, China

    Wing-Leung Wong & Cheuk-Fai Chow

Authors
  1. Jue Wang
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  2. Chunya Li
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  3. Wing-Leung Wong
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  4. Cheuk-Fai Chow
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Correspondence to Chunya Li.

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Published in Russian in Elektrokhimiya, 2018, Vol. 54, No. 12, pp. 1111–1123.

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Wang, J., Li, C., Wong, WL. et al. Novel Iron-Based Polynuclear Metal Complexes [FeII(L)(CN)4]2–[FeIII(H2O)3Cl]2: Synthesis and Study of Photovoltaic Properties for Dye-Sensitized Solar Cell. Russ J Electrochem 54, 1164–1175 (2018). https://doi.org/10.1134/S1023193518140094

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  • DOI: https://doi.org/10.1134/S1023193518140094

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