Synthesis and Photoluminescence Properties of Alkylbromoporphyrin

Ari Yustisia Akbar; Tania Avianda Gusman

doi:10.20961/jkpk.v6i3.56927

Synthesis and Photoluminescence Properties of Alkylbromoporphyrin

Ari Yustisia Akbar, Tania Avianda Gusman

Abstract

The usage of porphyrin as a light-harvesting chromophore is considered as one of the keys to obtaining low-cost and high-efficiency dye-sensitized solar cell (DSSC). In this paper, a novel porphyrin, 5,10,15-tris(nitrophenyl)-20-(p-(11-bromo)dodecoxyphenyl))porphyrin, having a long alkyl chain and three nitro groups was synthesized. The nitro groups serve as anchoring groups to TiO₂ surfaces and long alkyl chain prevents unwanted dye aggregation. The porphyrin was synthesized by condensation of p-(12-Bromododecoxy)benzaldehyde and pyrrole in propionic acid according to an adaptation of the general Rothemund method [1]. p-(12-Bromododecoxy)benzaldehyde was synthesized by nucleophilic substitution reaction between 4-hydroxybenzaldehyde and 1,12-dibromododecane in acetone. The reaction products were analyzed by ¹H-NMR and mass spectroscopy. The absorption and fluorescence spectra of the porphyrin were also recorded. As results, the absorption spectrum of the porphyrin consists of a strong Soret and four weak Q-band. Compared to 5,10,15-tris(nitrophenyl)-20-(p-(11-bromo)dodecoxyphenyl))porphyrin spectrum, there is no wavelength shifting because of the incorporation of the alkyl chain. The fluorescence spectrum of the porphyrin shows two characteristic emission bands and the intensity ratio of those emission bands is always constant when irradiated by different excitation wavelength related to Soret and Q-band.

Keywords

DSSC; porphyrin; absorption spectrum; emission spectrum.

Full Text:

PDF

References

[1] P. Rothemund, “Porphyrin Studies. III. The Structure of the Porphine Ring System”, Journal of the American Chemical Society. 61 (1939) 2912–2915.
doi: 10.1021/ja01265a096.

[2] K. Ladomenou, T. N. Kitsopoulos, G. D. Sharma, and A. G. Coutsolelos, “The importance of various anchoring groups attached on porphyrins as potential dyes for DSSC applications,” RSC Adv., vol. 4, no. 41, pp. 21379–21404, May 2014,
doi: 10.1039/C4RA00985A

[3] A. Shiotari, Y. Ozaki, S. Naruse, H. Okuyama, S. Hatta, T. Aruga, T. Tamaki, and T. Ogawa, Real-space characterization of hydroxyphenyl porphyrin derivatives designed for single-molecule devices, RSC Adv. 5 (2015) 79152–79156,
doi: 10.1039/C5RA12123J.

[4] K. Sharma, V. Sharma, and S.S. Sharma, Dye-Sensitized Solar Cells: Fundamentals and Current Status, Nanoscale Research Letters 2018 13:1. 13 (2018) 1–46.
doi: 10.1186/S11671-018-2760-6.

[5] K. Zeng, Y. Lu, W. Tang, S. Zhao, Q. Liu, W. Zhu, H. Tian, and Y. Xie, Efficient solar cells sensitized by a promising new type of porphyrin: dye-aggregation suppressed by double strapping, Chemical Science. 10 (2019) 2186–2192.
doi: 10.1039/C8SC04969F.

[6] Q. Wang, W.M. Campbell, E.E. Bonfantani, K.W. Jolley, D.L. Officer, P.J. Walsh, K. Gordon, R. Humphry-Baker, M.K. Nazeeruddin, and M. Grätzel, Efficient light harvesting by using green Zn-porphyrin-sensitized nanocrystalline TiO₂ films, Journal of Physical Chemistry B. 109 (2005) 15397–15409.
doi: 10.1021/jp052877w.

[7] W.M. Campbell, K.W. Jolley, P. Wagner, K. Wagner, P.J. Walsh, K.C. Gordon, L. Schmidt-Mende, M.K. Nazeeruddin, Q. Wang, M. Grätzel, and D.L. Officer, Highly efficient porphyrin sensitizers for dye-sensitized solar cells, Journal of Physical Chemistry C. 111 (2007) 11760–11762.
doi: 10.1021/JP0750598.

[8] L. Si, H. He, and K. Zhu, 8-Hydroxylquinoline-conjugated porphyrins as broadband light absorbers for dye-sensitized solar cells, New Journal of Chemistry. 38 (2014) 1565–1572.
doi: 10.1039/C3NJ01643A.

[9] F. Odobel, E. Blart, M. Lagrée, M. Villieras, H. Boujtita, N. el Murr, S. Caramori, and C.A. Bignozzi, Porphyrin dyes for TiO2 sensitization, Journal of Materials Chemistry. 13 (2003) 502–510.
doi: 10.1039/B210674D.

[10] J. Cong, X. Yang, J. Liu, J. Zhao, Y. Hao, Y. Wang, and L. Sun, Nitro group as a new anchoring group for organic dyes in dye-sensitized solar cells, Chemical Communications. 48 (2012) 6663–6665.
doi: 10.1039/C2CC31516E.

[11] H. Chen, G. Lyu, Y. Yue, T. Wang, D.P. Li, H. Shi, J. Xing, J. Shao, R. Zhang, and J. Liu, Improving the photovoltaic performance by employing alkyl chains perpendicular to the π-conjugated plane of an organic dye in dye-sensitized solar cells, Journal of Materials Chemistry C. 7 (2019) 7249–7258.
doi: 10.1039/C9TC01520E.

[12] Y.H. Lee, R.K. Chitumalla, B.Y. Jang, J. Jang, S. Thogiti, and J.H. Kim, Alkyl chain length dependence of the charge-transfer, recombination and electron diffusion length on the photovoltaic performance in double donor-acceptor-based organic dyes for dye sensitized solar cells, Dyes and Pigments. 133 (2016) 161–172.
doi: 10.1016/J.DYEPIG.2016.05.035.

[13] D. Joly, M. Godfroy, L. Pellejà, Y. Kervella, P. Maldivi, S. Narbey, F. Oswald, E. Palomares, and R. Demadrille, Side chain engineering of organic sensitizers for dye-sensitized solar cells: a strategy to improve performances and stability, Journal of Materials Chemistry A. 5 (2017) 6122–6130.
doi: 10.1039/C7TA00793K.

[14] J.S. Lindsey, I.C. Schreiman, H.C. Hsu, P.C. Kearney, and A.M. Marguerettaz, Rothemund and Adler-Longo reactions revisited: synthesis of tetraphenylporphyrins under equilibrium conditions, The Journal of Organic Chemistry. 52 (1987) 827–836.
doi: 10.1021/jo00381a022.

[15] R.E. Falvo, L.M. Mink, and D.F. Marsh, Microscale Synthesis and 1H NMR Analysis of Tetraphenylporphyrins, Journal of Chemical Education. 76 (1999) 237–239.
doi: https://doi.org/10.1021/ed076p237

[16] R. Luguya, L. Jaquinod, F.R. Fronczek, M.G.H. Vicente, and K.M. Smith, Synthesis and reactions of meso-(p-nitrophenyl)porphyrins, Tetrahedron. 60 (2004) 2757–2763.
doi: 10.1016/j.tet.2004.01.080.

[17] G.Z.G. Meng, B.R. James, and K. a Skov, Porphyrin Chemistry Pertaining to the Design of Anticancer Drugs. 1. The Synthesis of Porphyrins Containing Meso-Pyridyl and Meso-Substituted Phenyl Functional-Groups, Can. J. Chem. 72 (1994) 1894–1909.
doi: 10.1139/v94-241.

[18] W.J. Kruper, T.A. Chamberlin, and M. Kochanny, “Regiospecific Aryl Nitration of Meso-Subtituted Tetraarylporphyrins: A simple Route to Bifunctional Porphyrins”, Journal of Organic Chemistry. 54 (1989) 2753–2756.
Doi: https://doi.org/10.1021/jo00272a057

[19] E. Hasegawa, J.I. Nemoto, T. Kanayama, and E. Tsuchida, Syntheses and properties of vinyl monomers containing a meso-tetraphenylporphin ring and their copolymers, European Polymer Journal. 14 (1978) 123–127.
doi: 10.1016/0014-3057(78)90076-9.

[20] R.J. Abraham, M.A. Warne, and L. Griffiths, Proton chemical shifts in NMR. Part 10.1 Bromine and iodine substituent chemical shifts (SCS) and an analysis of the contributions to the SCS in halocyclohexanes, Journal of the Chemical Society. Perkin Transactions 2. (1997) 2151–2160.
doi: 10.1039/A704537I.

[21] S.V.D. Nicholas W. Smith, Efficient nitration of meso- tetraphenylporphyrin with nitronium tetrafluoroborate, Arkivoc. 7 (2010) 10–18.
doi: 10.3998/ark.5550190.0011.702

[22] M. Uttamlal, and A. Sheila Holmes-Smith, The excitation wavelength dependent fluorescence of porphyrins, Chemical Physics Letters. 454 (2008) 223–228.
doi:10.1016/J.CPLETT.2008.02.012.

[23] A. Lukaszewicz, J. Karolczak, D. Kowalska, A. Maciejewski, M. Ziolek, and R.P. Steer, Photophysical processes in electronic states of zinc tetraphenyl porphyrin accessed on one- and two-photon excitation in the soret region, Chemical Physics. 331 (2007) 359–372.
doi: 10.1016/J.CHEMPHYS.2006.11.006.

DOI: https://doi.org/10.20961/jkpk.v6i3.56927