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Synthesis and photochromic behaviour of a series of benzopyrans bearing an N-phenyl-carbazole moiety: photochromism control by the steric effect

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Abstract

Five new N-phenyl-carbazole benzopyrans bearing different substitutions on one of the phenyl rings at the sp3 carbon have been synthesized. Their molecular structures were investigated by X-ray and NMR analyses and through quantum chemical calculations. The photochromic mechanism under UV irradiation in toluene, consisting of the consecutive formation of transoid-cis (TC) and transoid-trans (TT) isomers, was studied by UV-vis spectral and kinetic analyses. These molecules have been specifically designed to ascertain the possibility of favouring the formation of the less thermodynamically stable TT at the photostationary state, upon exploiting steric hindrance effects on the diene part of the molecule. The spectrokinetic study allowed the estimation of most of the spectrokinetic parameters, such as molar extinction coefficients, quantum yields of UV colouration and visible photobleaching, and the rate constants of the fast and slow thermal bleaching processes. Peculiar effects of substituents with different donor strengths on one phenyl ring located at the 3-position were observed on the spectrokinetic properties.

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References

  1. B. Van Gemert, in Organic Photochromic and Thermochromic Compounds, ed. J. C. Crano and R. J. Guglielmetti, Kluwer Academic/Plenum Publishers, New York, 1999, vol. 1, pp. 111–140.

  2. J. D. Hepworth and B. M. Heron, in Functional Dyes, ed. S.-H. Kim, Amsterdam, Elsevier, 2006, pp. 85–135.

  3. N. S. Corns, S. M. Partington and A. D. Towns, Industrial organic photochromic dyes, Color. Technol., 2009, 125, 249–261.

    Article  CAS  Google Scholar 

  4. J. Kolc and R. S. Becker, Proof of structure of the colored photoproducts of chromenes and spiropyrans, J. Phys. Chem., 1967, 71, 4045–4048.

    Article  CAS  Google Scholar 

  5. C. Lenoble and R. S. Becker, Photophysics, photochemistry and kinetics of photochromic 2H-pyrans and chromenes, J. Photochem., 1986, 33, 187–197.

    Article  CAS  Google Scholar 

  6. H. Bouas-Laurent and H. Dürr, Organic photochromism, Pure Appl. Chem., 2001, 73, 639–665.

    Article  CAS  Google Scholar 

  7. G. Ottavi, G. Favaro and V. Malatesta, Spectrokinetic study of 2,2–diphenyl-5,6-benzo(2H)chromene: a thermoreversible and photoreversible photochromic system, J. Photochem. Photobiol., A, 1998, 115, 123–128.

    Article  CAS  Google Scholar 

  8. S. Delbaere, G. Vermeersch and J.-C. Micheau, Quantitative analysis of the dynamic behaviour of photochromic systems, J. Photochem. Photobiol., C, 2011, 12, 74–105.

    Article  CAS  Google Scholar 

  9. R Demadrille, A. Rabourdin, M. Campredon and G. Giusti, Spectroscopic characterisation and photodegradation studies of photochromic spiro[fluorene-9,3′-[3′H]-naphtho[2,1-b] pyrans], J. Photochem. Photobiol., A, 2004, 168, 143–152.

    Article  CAS  Google Scholar 

  10. C. D. Gabbutt, M. Heron, A. C. Instone, S. B. Kolla, K. Mahajan, P. J. Coelho and L. M. Carvalho, Synthesis and photochromic properties of symmetrical aryl ether linked bi- and tri-naphthopyrans, Dyes Pigm., 2008, 76, 24–34.

    Article  Google Scholar 

  11. R. S. Becker and J. Michl, Photochromism of Synthetic and Naturally Occurring 2H-Chromenes and 2H-Pyrans, J. Am. Chem. Soc., 1966, 88, 5931–5933.

    Article  CAS  Google Scholar 

  12. B. Luccioni-Houze, M. Campredon, R. Guglielmetti and G. Giusti, Kinetic Analysis of Fluoro-[2 h]-Chromenes at the Photostationary States, Mol. Cryst. Liq. Cryst., 1997, 297, 161–165.

    Article  CAS  Google Scholar 

  13. J. J. Luthem, The Effect of Substituents on the Ring Closure Reaction of Photo Activated Diarylnaphthopyrans, Mol. Cryst. Liq. Cryst., 1997, 297, 155–160.

    Article  Google Scholar 

  14. A. Kumar, The Relationship Between the Structure and the Absorption Spectra of Naphtho[2,1-B]pyran, Mol. Cryst. Liq. Cryst., 1997, 297, 139–145.

    Article  CAS  Google Scholar 

  15. J. Hobley, V. Malatesta, R. Millini, W. Giroldini, L. Wis, M. Goto, M. Kishimotoa and H. Fukumura, Photochromism of chromene crystals; a new property of old chromenes, Chem. Commun., 2000, 1339–1340.

  16. J. Aubard, F. Maurel, G. Buntinx, O. Poizat, G. Levi, R. Guglielmetti and A. Samat, Femto/Picosecond Transient Absorption Spectroscopy of Photochromic 3,3-Diphenylnaphtho[2,1-b]pyran, Mol. Cryst. Liq. Cryst., 2000, 345, 215–220.

    Article  CAS  Google Scholar 

  17. S. Delbaere and G. Vermeersch, NMR characterization of allenyl-naphthol in the photochromic process of 3,3-diphenyl-[3H]-naphtho[2-1,b]pyran, J. Photochem. Photobiol., A, 2003, 159, 227–232.

    Article  CAS  Google Scholar 

  18. P. L. Gentili, E. Danilov, F. Ortica, M. A. J. Rodgers and G. Favaro, Dynamics of the excited states of chromenes studied by fast and ultrafast spectroscopies, Photochem. Photobiol. Sci., 2004, 3, 886–891.

    Article  CAS  Google Scholar 

  19. R. G. Brown, M. Maafl, P. Foggi and L. Bussotti, The ultrafast dynamics of some photochromic naphthopyrans, in Femtochemistry and Femtobiology, ed. M. M. Martin and J. T. Hynes, 2004, 283–286.

  20. F. Maurel, S. Lau Truong, J. P. Bertigny, R. Dubest, G. Lévi, J. Aubard, S. Delbaere and G. Vermeersch, SERS Study of 3,3-Diphenyl-naphtho[2,1-b]pyran: Another Evidence for Allenyl-Naphthol Involvement in the Photochromic Mechanism, Mol. Cryst. Liq. Cryst., 2005, 430, 235–241.

    Article  CAS  Google Scholar 

  21. B. Moine, G. Buntinx, O. Poizat, J. Rehault, C. Moustrou and A. Samat, Transient absorption investigation of the photophysical properties of new photochromic 3H-naphtho [2,1-b]pyran, J. Phys. Org. Chem., 2007, 20, 936–943.

    Article  CAS  Google Scholar 

  22. B. Moine, J. Réhault, S. Aloïse, J.-C. Micheau, C. Moustrou, A. Samat, O. Poizat and G. Buntinx, Transient Absorption Studies of the Photochromic Behavior of 3H-Naphtho[2,1-b]pyrans Linked to Thiophene Oligomers via an Acetylenic Junction, J. Phys. Chem. A, 2008, 112, 4719–4726.

    Article  CAS  Google Scholar 

  23. J. Harada, K. Ueki, M. Anada, Y. Kawazoe and K. Ogawa, Solid-state Photochromism of Chromenes: Enhanced Photocoloration and Observation of Unstable Colored Species at Low Temperatures, Chem. – Eur. J., 2011, 17, 14111–14119.

    Article  CAS  Google Scholar 

  24. T. T. Herzog, G. Ryseck, E. Ploetz and T. Cordes, The photochemical ring opening reaction of chromene as seen by transient absorption and fluorescence spectroscopy, Photochem. Photobiol. Sci., 2013, 12, 1202–1209.

    Article  CAS  Google Scholar 

  25. Y. Inagaki, Y. Kobayashi, K. Mutoh and J. Abe, A Simple and Versatile Strategy for Rapid Color Fading and Intense Coloration of Photochromic Naphthopyran Families, J. Am. Chem. Soc., 2017, 139, 13429–13441.

    Article  CAS  Google Scholar 

  26. S. Brazevic, S. Nizinski, R. Szabla, M. F. Rode and G. Burdzinski, Photochromic reaction in 3H-naphthopyrans studied by vibrational spectroscopy and quantum chemical calculations, Phys. Chem. Chem. Phys., 2019, 21, 11861–11870.

    Article  CAS  Google Scholar 

  27. S. Brazevic, M. Baranowski, M. Sikorski, M. Rode and G. Burdzinski, Ultrafast dynamics of the transoid-cis isomer formed in photochromic reaction from 3H-naphthopyran, ChemPhysChem, 2020, 21, 1402–1407.

    Article  CAS  Google Scholar 

  28. C. M. Sousa, J. Berthet, S. Delbaere and P. J. Coelho, Synthesis of 1-Vinylidene-naphthofurans: A Thermally Reversible Photochromic System That Colors Only When Adsorbed on Silica Gel, J. Org. Chem., 2013, 78, 6956–6961.

    Article  CAS  Google Scholar 

  29. C. Sousa, S. Saraiva, H. Macedo and P. Coelho, Grey colouring thermally reversible photochromic 1-vinylidenenaphthofurans, Dyes Pigm., 2017, 141, 269–276.

    Article  CAS  Google Scholar 

  30. C. M. Sousa, J. Berthet, S. Delbaere, A. Polonia and P. J. Coelho, Control of the Switching Speed of Photochromic Naphthopyrans through Restriction of Double Bond Isomerization, J. Org. Chem., 2017, 82, 12028–12037.

    Article  CAS  Google Scholar 

  31. C. M. Sousa and P. J. Coelho, Joining High Coloration and Fast Color Fading with Photochromic Fused-Naphthopyrans, Eur. J. Org. Chem., 2020, 985–992.

  32. H. Kuroiwa, Y. Inagaki, K. Mutoh and J. Abe, On-Demand Control of the Photochromic Properties of Naphthopyrans, Adv. Mater., 2019, 31, 1805661.

    Article  Google Scholar 

  33. M. Frigoli, F. Maurel, J. Berthet, S. Delbaere, J. Marrot and M. M. Oliveira, The Control of Photochromism of [3H]-Naphthopyran Derivatives with Intramolecular CH-π Bonds, Org. Lett., 2012, 14, 4150–4153.

    Article  CAS  Google Scholar 

  34. M. Frigoli, J. Marrot, P. L. Gentili, D. Jacquemin, M. Vagnini, D. Pannacci and F. Ortica, P-type Photochromism of new Helical Naphthopyrans: Synthesis, and Photochemical, Photophysical and Theoretical Study, ChemPhysChem, 2015, 16, 2447–2458.

    Article  CAS  Google Scholar 

  35. F. Ianni, S. Scorzoni, P. L. Gentili, A. Di Michele, M. Frigoli, E. Camaioni, F. Ortica and R. Sardella, Chiral separation of helical chromenes with chloromethyl phenylcarbamate polysaccharide-based stationary phases, J. Sep. Sci., 2018, 41, 1266–1273.

    Article  CAS  Google Scholar 

  36. S. R. Meech and D. Phillips, Photophysics of some common fluorescence standards, J. Photochem., 1983, 23, 193–217.

    Article  CAS  Google Scholar 

  37. M. M. Oliveira, M. A. Salvador, P. J. Coelho and L. M. Carvalho, New benzopyranocarbazoles: synthesis and photochromic behavior, Tetrahedron, 2005, 61, 1681–1691.

    Article  CAS  Google Scholar 

  38. J. C. Antilla, A. Klapars and S. L. Buchwald, The Copper-Catalyzed N-Arylation of Indoles, J. Am. Chem. Soc., 2002, 124, 11684–11688.

    Article  CAS  Google Scholar 

  39. J. Pang, Y. Tao, S. Freiberg, X.-P. Yang, M. D’Iorioa and S. Wang, Syntheses, structures, and electroluminescence of new blue luminescent star-shaped compounds based on 1,3,5-triazine and 1,3,5-trisubstituted benzene, J. Mater. Chem., 2002, 12, 206–212.

    Article  CAS  Google Scholar 

  40. M. M. Oliveira, M. A. Salvador, S. Delbaere, J. Berthet, G. Vermeersch, J. C. Micheau, P. J. Coelho and L. M. Carvalho, Remarkable thermally stable open forms of photochromic new N-substituted benzopyranocarbazoles, J. Photochem. Photobiol., A, 2008, 198, 242–249.

    Article  CAS  Google Scholar 

  41. P. R. Andrews, S. L. A. Munro, M. Sadek and M. G. Wong, The hybridization state of nitrogen as a conformational variable in biologically active molecules, J. Chem. Soc., Perkin Trans. 2, 1988, 711–718.

  42. I. B. Berlman, Handbook of fluorescence spectra of aromatic molecules, Academic Press, 1971, p. 213.

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Authors and Affiliations

  1. Universite Paris-Saclay, UVSQ, UMR CNRS 8080, Institut Lavoisier de Versailles, 45 av des Etats-Unis, 78035, Versailles, France

    Michel Frigoli, Tanguy Jousselin-Oba & Jérôme Marrot

  2. Center for Organic Photonics and Electronics Research (OPERA), JST ERATO Adachi Molecular Exciton Engineering Project, and Academia-Industry Molecular Systems for Devices Research and Education Center, Kyushu University, Nishi, Fukuoka, 819-0395, Japan

    Masashi Mamada & Chihaya Adachi

  3. Dipartimento di Chimica, Biologia e Biotecnologie, Universita degli Studi di Perugia, Via Elce di Sotto 8, 06123, Perugia, Italy

    Agnese Zangarelli, Danilo Pannacci & Fausto Ortica

  4. International Institute for Carbon Neutral Energy Research (WPI-I2CNER), Kyushu University, Nishi, Fukuoka, 819-0395, Japan

    Chihaya Adachi

  5. Istituto Nazionale di Fisica Nucleare (INFN), Sezione di Perugia, Via Pascoli, 06123, Perugia, Italy

    Fausto Ortica

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  1. Michel Frigoli
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  2. Tanguy Jousselin-Oba
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Correspondence to Michel Frigoli.

Additional information

Electronic supplementary information (ESI) available. CCDC 1998515. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/d0pp00202j

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Frigoli, M., Jousselin-Oba, T., Mamada, M. et al. Synthesis and photochromic behaviour of a series of benzopyrans bearing an N-phenyl-carbazole moiety: photochromism control by the steric effect. Photochem Photobiol Sci 19, 1344–1355 (2020). https://doi.org/10.1039/d0pp00202j

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