Theoretical approach for Fe(II/III) and its chlorophyll-related complexes as sensitizers in dye-sensitized solar cells

Keywords: Chlorophyll, DSSC, DFT, MLCT, d orbital, non-innocence ligand, ligand radical cation


Dye is the key to the efficiency of harvesting solar energy in dye-sensitized solar cells (DSSCs). The dye performances such as light absorption, electron injection, and electron regeneration depend on the dye molecule structure. To predict it, one needs to compute the optimized molecule geometry, HOMO level, LUMO level, electron density distribution, energy gaps, and dipole moment in the ground and excited state. Chlorophyll-related chlorin and porphyrin, as well as their κ2O,O’ complexes with Fe(II/III), were investigated with density functional theory (DFT) and time-dependent density functional theory (TD-DFT) computations using the B3LYP method and def2-TZVP basis set. NPA charges also were calculated to know the valence of the metal cations exactly. In general, the calculations show that the metal cations introduced occupied d orbitals with lower oxidation potentials than the chlorophyll ligand orbitals, which are responsible for the emergence of additional absorption bands. The states result in effective band broadening and the redshift of spectrum absorbance that is expected to improve DSSC performance.

Another requirement that has to be possessed is the ability of electron regeneration, electron injection, and dipole moment. The Fe(II) complex has fulfilled these requirements, but not the Fe(III) complex due to having a low electron injection capability. However, this work has shown that Fe(III) complex exhibits a non-innocence ligand. It results in trivalent to divalent state change, in the appearance of a ligand radical cation, an extra hole, and a broader absorption spectrum. It also can affect its other electronic properties, such as electron injection capability. Thus, it can be considered an attractive candidate for the sensitizer in DSSCs


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Author Biographies

Mohamad Rodhi Faiz, Brawijaya University; State University of Malang

Department of Mechanical Engineering

Department of Electrical Engineering

Denny Widhiyanuriyawan, Brawijaya University

Department of Mechanical Engineering

Eko Siswanto, Brawijaya University

Department of Mechanical Engineering

Fazira Ilyana Abdul Razak, Universiti Teknologi Malaysia

Department of Chemistry

I Nyoman Gede Wardana, Brawijaya University

Department of Mechanical Engineering


Lewis, N. S., Crabtree, G., Nozik, A. J., Wasielewski, M. R., Alivisatos, P., Kung, H. et. al. (2005). Basic Research Needs for Solar Energy Utilization. Report of the Basic Energy Sciences Workshop on Solar Energy Utilization. U.S. Department of Energy Office of Scientific and Technical Information. doi:

Wu, C., Wang, K., Batmunkh, M., Bati, A. S. R., Yang, D., Jiang, Y. et. al. (2020). Multifunctional nanostructured materials for next generation photovoltaics. Nano Energy, 70, 104480. doi:

Babar, F., Mehmood, U., Asghar, H., Mehdi, M. H., Khan, A. U. H., Khalid, H. et. al. (2020). Nanostructured photoanode materials and their deposition methods for efficient and economical third generation dye-sensitized solar cells: A comprehensive review. Renewable and Sustainable Energy Reviews, 129, 109919. doi:

O’Regan, B., Grätzel, M. (1991). A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature, 353 (6346), 737–740. doi:

Odobel, F., Pellegrin, Y., Gibson, E. A., Hagfeldt, A., Smeigh, A. L., Hammarström, L. (2012). Recent advances and future directions to optimize the performances of p-type dye-sensitized solar cells. Coordination Chemistry Reviews, 256 (21-22), 2414–2423. doi:

Al-Ghamdi, A. A., Gupta, R. K., Kahol, P. K., Wageh, S., Al-Turki, Y. A., El Shirbeeny, W., Yakuphanoglu, F. (2014). Improved solar efficiency by introducing graphene oxide in purple cabbage dye sensitized TiO2 based solar cell. Solid State Communications, 183, 56–59. doi:

Syafinar, R., Gomesh, N., Irwanto, M., Fareq, M., Irwan, Y. M. (2015). Chlorophyll Pigments as Nature Based Dye for Dye-Sensitized Solar Cell (DSSC). Energy Procedia, 79, 896–902. doi:

Tamiaki, H., Tsuji, K., Kuno, M., Kimura, Y., Watanabe, H., Miyatake, T. (2016). Synthesis of chlorophyll- a derivatives methylated in the 3-vinyl group and their intrinsic site energy. Bioorganic & Medicinal Chemistry Letters, 26 (13), 3034–3037. doi:

Refat, M. S. (2013). Synthesis and characterization of ligational behavior of curcumin drug towards some transition metal ions: Chelation effect on their thermal stability and biological activity. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 105, 326–337. doi:

Shalini, S., Balasundara prabhu, R., Prasanna, S., Mallick, T. K., Senthilarasu, S. (2015). Review on natural dye sensitized solar cells: Operation, materials and methods. Renewable and Sustainable Energy Reviews, 51, 1306–1325. doi:

Arkan, F., Izadyar, M. (2017). The investigation of the central metal effects on the porphyrin-based DSSCs performance; molecular approach. Materials Chemistry and Physics, 196, 142–152. doi:

Arkan, F., Izadyar, M., Nakhaeipour, A. (2016). The role of the electronic structure and solvent in the dye-sensitized solar cells based on Zn-porphyrins: Theoretical study. Energy, 114, 559–567. doi:

Özkan, G., Ersus Bilek, S. (2015). Enzyme-assisted extraction of stabilized chlorophyll from spinach. Food Chemistry, 176, 152–157. doi:

Han, J., Wang, Y., Ma, J., Wu, Y., Hu, Y., Ni, L., Li, Y. (2013). Simultaneous aqueous two-phase extraction and saponification reaction of chlorophyll from silkworm excrement. Separation and Purification Technology, 115, 51–56. doi:

Çakar, S., Özacar, M. (2019). The pH dependent tannic acid and Fe-tannic acid complex dye for dye sensitized solar cell applications. Journal of Photochemistry and Photobiology A: Chemistry, 371, 282–291. doi:

Çakar, S. (2019). 1,10 phenanthroline 5,6 diol metal complex (Cu, Fe) sensitized solar cells: A cocktail dye effect. Journal of Power Sources, 435, 226825. doi:

Wang, D., Sun, Y., Shang, Q., Wang, X., Guo, T., Guan, H., Lu, Q. (2017). Effects of the conjugated structure of Fe–bipyridyl complexes on photoinduced electron transfer in TiO2 photocatalytic systems. Journal of Catalysis, 356, 32–42. doi:

Ferreira, H., von Eschwege, K. G., Conradie, J. (2016). Electronic properties of Fe charge transfer complexes – A combined experimental and theoretical approach. Electrochimica Acta, 216, 339–346. doi:

Setyawati, H., Darmokoesoemo, H., Ningtyas, A. T. A., Kadmi, Y., Elmsellem, H., Kusuma, H. S. (2017). Effect of metal ion Fe(III) on the performance of chlorophyll as photosensitizers on dye sensitized solar cell. Results in Physics, 7, 2907–2918. doi:

Lu, Y.-H., Liu, R.-R., Zhu, K.-L., Song, Y.-L., Geng, Z.-Y. (2016). Theoretical study on the application of double-donor branched organic dyes in dye-sensitized solar cells. Materials Chemistry and Physics, 181, 284–294. doi:

Ren, X., Jiang, S., Cha, M., Zhou, G., Wang, Z.-S. (2012). Thiophene-Bridged Double D-π-A Dye for Efficient Dye-Sensitized Solar Cell. Chemistry of Materials, 24 (17), 3493–3499. doi:

Preat, J., Jacquemin, D., Perpète, E. A. (2010). Towards new efficient dye-sensitised solar cells. Energy & Environmental Science, 3 (7), 891. doi:

Zhang, J., Li, H.-B., Sun, S.-L., Geng, Y., Wu, Y., Su, Z.-M. (2012). Density functional theory characterization and design of high-performance diarylamine-fluorenedyes with different π spacers for dye-sensitized solar cells. J. Mater. Chem., 22 (2), 568–576. doi:

Fan, W., Tan, D., Deng, W.-Q. (2012). Acene-Modified Triphenylamine Dyes for Dye-Sensitized Solar Cells: A Computational Study. ChemPhysChem, 13 (8), 2051–2060. doi:

Preat, J., Jacquemin, D., Michaux, C., Perpète, E. A. (2010). Improvement of the efficiency of thiophene-bridged compounds for dye-sensitized solar cells. Chemical Physics, 376 (1-3), 56–68. doi:

Preat, J., Michaux, C., Jacquemin, D., Perpète, E. A. (2009). Enhanced Efficiency of Organic Dye-Sensitized Solar Cells: Triphenylamine Derivatives. The Journal of Physical Chemistry C, 113 (38), 16821–16833. doi:

Marinado, T., Nonomura, K., Nissfolk, J., Karlsson, M. K., Hagberg, D. P., Sun, L. et. al. (2009). How the Nature of Triphenylamine-Polyene Dyes in Dye-Sensitized Solar Cells Affects the Open-Circuit Voltage and Electron Lifetimes. Langmuir, 26 (4), 2592–2598. doi:

Lu, J., Meng, Q., Zhang, L., Liu, Y., Liu, W., Zhang, X. (2015). Single crystal structure, self-assembled nano-structure and semiconductor properties of a sandwich-type mixed (phthalocyaninato)(porphyrinato) europium triple-decker complex. Dyes and Pigments, 115, 1–6. doi:

Bechaieb, R., Ben Akacha, A., Gérard, H. (2016). Quantum chemistry insight into Mg-substitution in chlorophyll by toxic heavy metals: Cd, Hg and Pb. Chemical Physics Letters, 663, 27–32. doi:

Neese, F. (2011). The ORCA program system. WIREs Computational Molecular Science, 2 (1), 73–78. doi:

Neese, F. (2017). Software update: the ORCA program system, version 4.0. WIREs Computational Molecular Science, 8 (1). doi:

Neese, F., Wennmohs, F., Becker, U., Riplinger, C. (2020). The ORCA quantum chemistry program package. The Journal of Chemical Physics, 152 (22), 224108. doi:

Weigend, F., Ahlrichs, R. (2005). Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Physical Chemistry Chemical Physics, 7 (18), 3297. doi:

Schäfer, A., Horn, H., Ahlrichs, R. (1992). Fully optimized contracted Gaussian basis sets for atoms Li to Kr. The Journal of Chemical Physics, 97 (4), 2571–2577. doi:

Weigend, F. (2006). Accurate Coulomb-fitting basis sets for H to Rn. Physical Chemistry Chemical Physics, 8 (9), 1057. doi:

Becke, A. D. (1993). Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 98 (7), 5648–5652. doi:

Lee, C., Yang, W., Parr, R. G. (1988). Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Physical Review B, 37 (2), 785–789. doi:

Barone, V., Cossi, M. (1998). Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model. The Journal of Physical Chemistry A, 102 (11), 1995–2001. doi:

Andrae, D., Haeussermann, U., Dolg, M., Stoll, H., Preuss, H. (1990). Energy-adjustedab initio pseudopotentials for the second and third row transition elements. Theoretica Chimica Acta, 77 (2), 123–141. doi:

Neese, F. (2003). An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix. Journal of Computational Chemistry, 24 (14), 1740–1747. doi:

Neese, F., Wennmohs, F., Hansen, A., Becker, U. (2009). Efficient, approximate and parallel Hartree–Fock and hybrid DFT calculations. A “chain-of-spheres” algorithm for the Hartree–Fock exchange. Chemical Physics, 356 (1-3), 98–109. doi:

Nikolaienko, T. Y., Bulavin, L. A., Hovorun, D. M. (2014). JANPA: An open source cross-platform implementation of the Natural Population Analysis on the Java platform. Computational and Theoretical Chemistry, 1050, 15–22. doi:

Nikolaienko, T. Y., Bulavin, L. A. (2018). Localized orbitals for optimal decomposition of molecular properties. International Journal of Quantum Chemistry, 119 (3), e25798. doi:

Jaramillo, P., Coutinho, K., Cabral, B. J. C., Canuto, S. (2012). Ionization of chlorophyll-c2 in liquid methanol. Chemical Physics Letters, 546, 67–73. doi:

Kunieda, M., Tamiaki, H. (2008). Synthesis of Zinc 3-Hydroxymethyl-porphyrins Possessing Carbonyl Groups at the 13- and/or 15-Positions for Models of Self-Aggregative Chlorophylls in Green Photosynthetic Bacteria. The Journal of Organic Chemistry, 73 (19), 7686–7694. doi:

Bechaieb, R., Fredj, A. B., Akacha, A. B., Gérard, H. (2016). Interactions of copper(II) and zinc(II) with chlorophyll: insights from density functional theory studies. New Journal of Chemistry, 40 (5), 4543–4549. doi:

Wu, Z., Xu, Z., Tan, H., Li, X., Yan, J., Dong, C., Zhang, L. (2019). Two novel rhodamine-based fluorescent probes for the rapid and sensitive detection of Fe3+: Experimental and DFT calculations. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 213, 167–175. doi:

Chen, H., Wang, J., Zhao, F., Wang, Y., He, H., Xia, H. (2019). Synthesis, spectroscopic and DFT studies of copper(I) complexes inserting the electron-donating groups into pyridine-imidazole ligands vis an acetylide linker. Inorganica Chimica Acta, 498, 119155. doi:

Erden, I., Hatipoglu, A., Cebeci, C., Aydogdu, S. (2020). Synthesis of D-π-A type 4,5-diazafluorene ligands and Ru (II) complexes and theoretical approaches for dye-sensitive solar cell applications. Journal of Molecular Structure, 1201, 127202. doi:

Wang, C., Li, J., Cai, S., Ning, Z., Zhao, D., Zhang, Q., Su, J.-H. (2012). Performance improvement of dye-sensitizing solar cell by semi-rigid triarylamine-based donors. Dyes and Pigments, 94 (1), 40–48. doi:

Li, R., Lv, X., Shi, D., Zhou, D., Cheng, Y., Zhang, G., Wang, P. (2009). Dye-Sensitized Solar Cells Based on Organic Sensitizers with Different Conjugated Linkers: Furan, Bifuran, Thiophene, Bithiophene, Selenophene, and Biselenophene. The Journal of Physical Chemistry C, 113 (17), 7469–7479. doi:

El Mahdy, A. M., Halim, S. A., Taha, H. O. (2018). DFT and TD-DFT calculations of metallotetraphenylporphyrin and metallotetraphenylporphyrin fullerene complexes as potential dye sensitizers for solar cells. Journal of Molecular Structure, 1160, 415–427. doi:

Saito, K., Mitsuhashi, K., Ishikita, H. (2020). Dependence of the chlorophyll wavelength on the orientation of a charged group: Why does the accessory chlorophyll have a low site energy in photosystem II? Journal of Photochemistry and Photobiology A: Chemistry, 402, 112799. doi:

Nogueira, A. E., Ribeiro, L. S., Gorup, L. F., Silva, G. T. S. T., Silva, F. F. B., Ribeiro, C., Camargo, E. R. (2018). New Approach of the Oxidant Peroxo Method (OPM) Route to Obtain Ti(OH)4 Nanoparticles with High Photocatalytic Activity under Visible Radiation. International Journal of Photoenergy, 2018, 1–10. doi:

AL-Temimei, F. A., Omran Alkhayatt, A. H. (2020). A DFT/TD-DFT investigation on the efficiency of new dyes based on ethyl red dye as a dye-sensitized solar cell light-absorbing material. Optik, 208, 163920. doi:

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How to Cite
Faiz, M. R., Widhiyanuriyawan, D., Siswanto, E., Razak, F. I. A., & Wardana, I. N. G. (2022). Theoretical approach for Fe(II/III) and its chlorophyll-related complexes as sensitizers in dye-sensitized solar cells. EUREKA: Physics and Engineering, (4), 3-15.