Abstract
Photochromic compounds exhibit reversible transition between closed and open isomeric forms upon irradiation accompanied by change in their color. The two isomeric forms differ not only in absorption spectra, but also in various physical and chemical properties and find applications as optical switching and data storage materials. In this contribution we apply Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) to predict the equilibrium geometry and absorption spectra of a benchmark set of diarylethene based photochromic compounds in open and closed forms (before and after photocyclization). Comparison of the calculated Bond Length Alternation parameters with those available from the X-ray data indicates M05-2x functional to be the best method for geometry optimization when basis set includes polarization functions. We found M05 functional accurately predicts the maximum absorption wavelength when solvent is taken into account. We recommend combined theory level TD-M05/6-31G*/PCM//M05-2x/6-31G*/PCM for prediction of geometrical and spectral parameters of diarylethene derivatives.
Chapter PDF
Similar content being viewed by others
Keywords
References
Nakamura, S., Yokojima, S., Uchida, K., Tsujioka, T., Goldberg, A., Murakami, A., Shinoda, K., Mikami, M., Kobayashi, T., Kobatake, S., Matsuda, K., Irie, M.: Theoretical investigation on photochromic diarylethene: A short review. J. Photochem. Photobiol. A-Chem. 200, 10–18 (2008)
Yamaguchi, T., Takami, S., Irie, M.: Photochromic properties of 1,2-bis (6-substitute-2-methyl-1-benzofuran-3-yl) ethene derivatives. J. Photochem. Photobiol. A-Chem. 193, 146–152 (2008)
Yamaguchi, T., Uchida, K., Irie, M.: Photochromic properties of diarylethene derivatives having benzofuran and benzothiophene rings based on regioisomers. Bull. Chem. Soc. Jpn. 81, 644–652 (2008)
Gilat, S.L., Kawai, S.H., Lehn, J.M.: Light-Triggered Electrical and Optical Switching Devices. J. Chem. Soc.-Chem. Commun., 1439–1442 (1993)
Gilat, S.L., Kawai, S.H., Lehn, J.M.: Light-Triggered Electrical and Optical Switching Devices. Molecular Crystals and Liquid Crystals Science and Technology Section a-Molecular Crystals and Liquid Crystals 246, 323–326 (1994)
Gilat, S.L., Kawai, S.H., Lehn, J.M.: Light-Triggered Molecular Devices - Photochemical Switching of Optical and Electrochemical Properties in Molecular Wire Type Diarylethene Species. Chem.-Eur. J. 1, 275–284 (1995)
Irie, M.: Photochromism: Memories and switches - Introduction. Chemical Reviews 100, 1683 (2000)
Irie, M., Mohri, M.: Thermally Irreversible Photochromic Systems - Reversible Photocyclization of Diarylethene Derivatives. J. Org. Chem. 53, 803–808 (1988)
Nakayama, Y., Hayashi, K., Irie, M.: Thermally Irreversible Phtotchromic Systems - Reversible Photocyclization of Nonsymmetrical Diarylethene Derivatives Bull. Chem. Soc. Jpn. 64, 789–795 (1991)
Bartkowiak, W., Zalesny, R., Leszczynski, J.: Relation between bond-length alternation and two-photon absorption of a push-pull conjugated molecules: a quantum-chemical study. Chem. Phys. 287, 103–112 (2003)
BlanchardDesce, M., Alain, V., Bedworth, P.V., Marder, S.R., Fort, A., Runser, C., Barzoukas, M., Lebus, S., Wortmann, R.: Large quadratic hyperpolarizabilities with donor-acceptor polyenes exhibiting optimum bond length alternation: Correlation between structure and hyperpolarizability. Chem.-Eur. J. 3, 1091–1104 (1997)
Bourhill, G., Bredas, J.L., Cheng, L.T., Marder, S.R., Meyers, F., Perry, J.W., Tiemann, B.G.: Experimental Demonstration of the Dependence of the 1st Hyperpolarizability of Donor-Acceptor-Substituted Polyenes on the Ground-State Polarization and Bond-Length Alternation. J. Am. Chem. Soc. 116, 2619–2620 (1994)
Choi, C.H., Kertesz, M., Karpfen, A.: The effects of electron correlation on the degree of bond alternation and electronic structure of oligomers of polyacetylene. J. Chem. Phys. 107, 6712–6721 (1997)
Kirtman, B., Champagne, B., Bishop, D.M.: Electric field simulation of substituents in donor-acceptor polyenes: A comparison with ab initio predictions for dipole moments, polarizabilities, and hyperpolarizabilities. J. Am. Chem. Soc. 122, 8007–8012 (2000)
Meyers, F., Marder, S.R., Pierce, B.M., Bredas, J.L.: Electric-Field Modulated Nonlinear-Optical Properties of Donor-Acceptor Polyenes - Sum-Over-States Investigation of the Relationship Between Molecular Polarizabilities (Alpha, Beta, and Gamma) and Bond-Length Alternation. J. Am. Chem. Soc. 116, 10703–10714 (1994)
Jacquemin, D., Femenias, A., Chermette, H., Ciofini, I., Adamo, C., Andre, J.M., Perpete, E.A.: Assessment of several hybrid DFT functionals for the evaluation of bond length alternation of increasingly long oligomers. J. Phys. Chem. A 110, 5952–5959 (2006)
Jacquemin, D., Perpete, E.A.: Ab initio calculations of the colour of closed-ring diarylethenes: TD-DFT estimates for molecular switches. Chem. Phys. Lett. 429, 147–152 (2006)
Jacquemin, D., Perpete, E.A., Chermette, H., Ciofini, I., Adamo, C.: Comparison of theoretical approaches for computing the bond length alternation of polymethineimine. Chem. Phys. 332, 79–85 (2007)
Jacquemin, D., Perpete, E.A., Ciofini, I., Adamo, C.: Assessment of recently for the evaluation of the developed density functional approaches bond length alternation in polyacetylene. Chem. Phys. Lett. 405, 376–381 (2005)
Perpete, E.A., Jacquemin, D.: An ab initio scheme for quantitative predictions of the visible spectra of diarylethenes. J. Photochem. Photobiol. A-Chem. 187, 40–44 (2007)
Perpete, E.A., Maurel, F., Jacquemin, D.: TD-DFT investigation of diarylethene dyes with cyclopentene, dihydrothiophene, and dihydropyrrole bridges. J. Phys. Chem. A 111, 5528–5535 (2007)
Perrier, A., Maurel, F., Aubard, J.: Theoretical study of the electronic and optical properties of photochromic dithienylethene derivatives connected to small gold clusters. J. Phys. Chem. A 111, 9688–9698 (2007)
Perrier, A., Maurel, F., Aubard, J.: Theoretical investigation of the substituent effect on the electronic and optical properties of photochromic dithienylethene derivatives. J. Photochem. Photobiol. A-Chem. 189, 167–176 (2007)
Maurel, F., Perrier, A., Perpete, E.A., Jacquemin, D.: A theoretical study of the perfluoro-diarylethenes electronic spectra. J. Photochem. Photobiol. A-Chem. 199, 211–223 (2008)
Kobatake, S., Yamada, T., Uchida, K., Kato, N., Irie, M.: Photochromism of 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene in a single crystalline phase. J. Am. Chem. Soc. 121, 2380–2386 (1999)
Yamada, T., Kobatake, S., Irie, M.: Single-crystalline photochromism of diarylethene mixtures. Bull. Chem. Soc. Jpn. 75, 167–173 (2002)
Irie, M., Lifka, T., Kobatake, S., Kato, N.: Photochromism of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene in a single-crystalline phase. J. Am. Chem. Soc. 122, 4871–4876 (2000)
Kobatake, S., Shibata, K., Uchida, K., Irie, M.: Photochromism of 1,2-bis(2-ethyl-5-phenyl-3-thienyl)perfluorocyclopentene in a single-crystalline phase. Conrotatory thermal cycloreversion of the closed-ring isomer. J. Am. Chem. Soc. 122, 12135–12141 (2000)
Yamaguchi, T., Irie, M.: Photochromism of bis(2-alkyl-1-benzofuran-3-yl)perfluorocyclopentene derivatives. J. Org. Chem. 70, 10323–10328 (2005)
Peters, A., McDonald, R., Branda, N.R.: Regulating pi-conjugated pathways using a photochromic 1,2-dithienylcyclopentene. Chem. Commun., 2274–2275 (2002)
Shirinyan, V.Z., Krayshkin, M.M., Belenkii, L.I.: Photochromic dihetarylethenes. 8. A new approach to the synthesis of 3, 4-bis (2, 5-dimethyl-3-thienyl)furan-2, 5-dione as potential photochrome, 81 (January 2001); Khim. Geterotsiklicheskikh Soedin., 426 (2001)
Uchida, K., Nakayama, Y., Irie, M.: Thermally Irreversible Photochromic Systems - Reversible Photocyclization of 1,2-Bis(benzo[b]thiophen-3-yl)ethene Derivatives. Bull. Chem. Soc. Jpn. 63, 1311–1315 (1990)
Nakayama, Y., Hayashi, K., Irie, M.: Thermally Irreversible Photochromic Systems - Reversible Photocyclization of 1,2-Diselenenylethene and 1,2-Diindolylethene Derivatives. J. Org. Chem. 55, 2592–2596 (1990)
Uchida, K., Kido, Y., Yamaguchi, T., Irie, M.: Thermally irreversible photochromic systems. Reversible photocyclization of 2-(1-benzothiophen-3-yl)-3-(2 or 3-thienyl)maleimide derivatives. Bull. Chem. Soc. Jpn. 71, 1101–1108 (1998)
Fukaminato, T., Kawai, T., Kobatake, S., Irie, M.: Fluorescence of photochromic 1,2-bis(3-methyl-2-thienyl)ethene. J. Phys. Chem. B 107, 8372–8377 (2003)
Irie, M., Uchida, K., Eriguchi, T., Tsuzuki, H.: Photochromism of Single-Crystalline Diarylethenes. Chem. Lett., 899–900 (1995)
Irie, M., Sakemura, K., Okinaka, M., Uchida, K.: Photochromism of dithienylethenes with electron-donating substituents. J. Org. Chem. 60, 8305–8309 (1995)
Peters, A., Branda, N.R.: Electrochemically induced ring-closing of photochromic 1,2-dithienylcyclopentenes. Chem. Commun., 954–955 (2003)
Moriyama, Y., Matsuda, K., Tanifuji, N., Irie, S., Irie, M.: Electrochemical cyclization/cycloreversion reactions of diarylethenes. Org. Lett. 7, 3315–3318 (2005)
Hanazawa, M., Sumiya, R., Horikawa, Y., Irie, M.: Thermally Irreversible Photochromic Systems - Reversible Photocyclization of 1,2-Bis(2-methylbenzo[b]thiophen-3-yl)Perfluorocycloalkene Derivatives. J. Chem. Soc.-Chem. Commun., 206–207 (1992)
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2009 Springer-Verlag Berlin Heidelberg
About this paper
Cite this paper
Patel, P.D., Masunov, A.E. (2009). Time-Dependent Density Functional Theory Study of Structure-Property Relationships in Diarylethene Photochromic Compounds. In: Allen, G., Nabrzyski, J., Seidel, E., van Albada, G.D., Dongarra, J., Sloot, P.M.A. (eds) Computational Science – ICCS 2009. ICCS 2009. Lecture Notes in Computer Science, vol 5545. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-01973-9_24
Download citation
DOI: https://doi.org/10.1007/978-3-642-01973-9_24
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-01972-2
Online ISBN: 978-3-642-01973-9
eBook Packages: Computer ScienceComputer Science (R0)