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Regio- and stereospecific [2+2] photocyclodimerization of a crown-contain butadienyl dye via cation-induced self-assembly in solution

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Abstract

Self-assembled pseudocyclic structures consisting of two molecules of a crown-containing butadienyl dye and two Mg2+ ions readily undergo regio- and stereospecific [2+2] photocycloaddition in MeCN to produce a single cyclobutane stereoisomer in almost quantitative yield.

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Notes and references

  1. J.-M. Lehn, Supramolecular chemistry, Concepts and perspectives, VCH, Weinheim, etc., 1995.

    Google Scholar 

  2. M. V. Alfimov, S. P. Gromov, O. B. Stanislavskii, E. N. Ushakov and O. A. Fedorova, Crown-containing styryl dyes. 8. Cation-dependent concerted [2+2] autophotocycloaddition of photochromic 15-crown-5 ether betaines, Russ. Chem. Bull., 1993, 42, 1385.

    Article  Google Scholar 

  3. S. P. Gromov, O. A. Fedorova, E. N. Ushakov, A. V. Buevich and M. V. Alfimov, Crown ether styryl dyes. 15. Synthesis and two pathways of regio- and stereospecific cation-dependent [2+2] autophotocycloaddition of chromogenic 15-crown-5 ether betaines of quinoline series, Russ. Chem. Bull., 1995, 44, 2131

    Article  Google Scholar 

  4. S. P. Gromov, E. N. Ushakov, O. A. Fedorova, A. V. Buevich and M. V. Alfimov, Crown ether styryl dyes. 18. Synthesis, anion-“capped” complexes, and ion-selective stereospecific [2+2] autophotocycloaddition of pho- tochromic 18-crown-6 ethers, Russ. Chem. Bull., 1996, 45, 654

    Article  Google Scholar 

  5. S. P. Gromov, O. A. Fedorova, E. N. Ushakov, I. I. Baskin, A. V. Lindeman, E. V. Malysheva, T. A. Balashova, A. S. Arsen’ev and M. V. Alfimov, Crown ether styryl dyes. 24. Synthesis of multiphotochromic 15-crown-5 ethers with rigid spacers, their anion-“capped” complexes, and stereospecific [2+2] autophotocycloaddition, Russ. Chem. Bull., 1998, 47, 97

    Article  CAS  Google Scholar 

  6. S. P. Gromov, E. N. Ushakov, O. A. Fedorova, I. I. Baskin, A. V. Buevich, E. N. Andryukhina, M. V. Alfimov, D. Johnels, U. G. Edlund, J. K. Whitesell and M. A. Fox, Novel photoswitchable receptors: synthesis and cation-induced self-assembly into dimeric complexes leading to stereospecific [2+2]-photocycloaddition of styryl dyes containing a 15-crown-5 ether unit, J. Org. Chem., 2003, 68, 6115.

    Article  CAS  Google Scholar 

  7. F. D. Lewis, T. Wu, E. L. Burch, D. M. Bassani, J.-S. Yang, S. Schneider, W. Jaeger and R. L. Letsinger, Hybrid oligonucleotides containing stilbene units. Excimer fluorescence and photodimerization, J. A m. Chem. Soc., 1995, 117, 8785.

    Article  CAS  Google Scholar 

  8. W. Herrmann, S. Wehrle and G. Wenz, Supramolecular control of the photochemistry of stilbenes by cyclodextrins, Chem. Commun., 1997, 1709.

    Google Scholar 

  9. (a)_S. Y. Jon, Y. H. Ko, S. H. Park, H.-J. Kim and K. Kim, A facile, stereoselective [2+2] photoreaction mediated by cucurbit[8]uril, Chem. Commun., 2001, 1938

    Google Scholar 

  10. S. P. Gromov, A. I. Vedernikov, L. G. Kuz’mina, D. V. Kondratuk, S. K. Sazonov, Yu. A. Strelenko, M. V. Alfimov and J. A. K. Howard, Photocontrolled molecular assembler based on cucurbit[8]uril: [2+2]-autophotocycloaddition of styryl dyes in the solid state and in water, Eur. J. Org. Chem., 2010, 2587.

    Google Scholar 

  11. R. Kaliappan, L. S. Kaanumalle, A. Natarajan and V. Ramamurthy, Templating photodimerization of stilbazoles with water-soluble cal-ixarenes, Photochem. Photobiol. Sci., 2006, 5, 925.

    Article  CAS  Google Scholar 

  12. M. Yoshizawa, Y. Takeyama, T. Kusukawa and M. Fujita, Cavity-directed, highly stereoselective [2+2] photodimerization of olefins within self-assembled coordination cages, Angew. Chem., Int. Ed., 2002, 41, 1347.

  13. (a)_D. M. Bassani, V. Darcos, S. Mahony and J.-P. Desvergne, Supramolecular catalysis of olefin [2+2] photodimerization, J. A m. Chem. Soc., 2000, 122, 8795

    Article  CAS  Google Scholar 

  14. W. G. Skene, E. Couzigné and J.- M. Lehn, Supramolecular control of the template-induced selective photodimerization of 4-methyl-7-O-hexylcoumarin, Chem.–Eur. J., 2003, 9, 5560.

    Article  CAS  Google Scholar 

  15. D. G. Amirsakis, A. M. Elizarov, M. A. Garcia-Garibay, P. T. Glink, J. F. Stoddart, A. J. P. White and D. J. Williams, Diastereospecific photochemical dimerization of a stilbene-containing daisy chain monomer in solution as well as in the solid state, Angew. Chem., Int. Ed., 2003, 42, 1126.

    Article  CAS  Google Scholar 

  16. (a)_Y. Vida Pol, R. Suau, E. Perez-Inestrosa and D. M. Bassani, Synergistic effects in controlling excited-state photodimerisation using multiple supramolecular interactions, Chem. Commun., 2004, 1270

    Google Scholar 

  17. S. P. Gromov, A. I. Vedernikov, Yu. V. Fedorov, O. A. Fedorova, E. N. Andryukhina, N. E. Shepel’, Yu. A. Strelenko, D. Johnels, U. Edlund, J. Saltiel and M. V. Alfimov, Self-assembly of a (ben- zothiazolyl)ethenylbenzocrown ether into a sandwich complex and stereoselective [2+2] photocycloaddition, Russ. Chem. Bull., 2005, 54, 1569

    Article  CAS  Google Scholar 

  18. A. I. Vedernikov, S. K. Sazonov, P. S. Loginov, N. A. Lobova, M. V. Alfimov and S. P. Gromov, Hydrogen bonding- and stacking-induced stereospecific [2+2]-photocycloaddition within a pseudodimeric complex of two styryl dyes, Mendeleev Commun., 2007, 17, 29.

    Article  CAS  Google Scholar 

  19. B. H. O. Cook and W. J. Leigh, Photopericyclic reactions of conjugated dienes and trienes, in The chemistry of dienes and polyenes, ed. Z. Rappoport, John Wiley & Sons, Chichester, etc., 2000, vol. 2, ch. 3, pp. 197–255.

    Chapter  Google Scholar 

  20. G. M. J. Schmidt, Photodimerization in the solid state, Pure Appl. Chem., 1971, 27, 647.

  21. H. Hopf, H. Greiving, P. G. Jones and P. Bubenitschek, Topochemical reaction control in solution, Angew. Chem., Int. Ed. Engl., 1995, 34, 685.

  22. (a)_K. Vishnumurthy, T. N. Guru, Row and K. Venkatesan, Fluorine in crystal engineering: photodimerization of (1E,3E)-1-phenyl-4-pentafluorophenylbuta-1,3-dienes in the crystalline state, Photochem. Photobiol. Sci., 2002, 1, 427

    Article  CAS  Google Scholar 

  23. X. Gao, T. Friščić and L. R. MacGillivray, Supramolecular construction of molecular ladders in the solid state, Angew. Chem., Int. Ed., 2004, 43, 232.

  24. For dye 1 and its analogues having a sulfonatobenzyl N-substituent, the dissociation of dimers (dye⊙Mg2+)2 into monomers dye⊙Mg2+ in anhydrous MeCN at a temperature of ca. 20 °C occurs within a characteristic time ranging from a few tens of seconds to a few minutes, which attests relatively strong intermolecular bonding in the dimers: (a) E. N. Ushakov, O. B. Stanislavskii, S. P. Gromov, O. A. Fedorova and M. V. Alfimov, Crown-containing styryl dyes. 6. Photoinduced and dark cation-dependent dimerization of betaines of photochromic 15-crown-5 ethers, Dokl. Phys. Chem., 1992, 323, 164

    Google Scholar 

  25. E. N. Ushakov, S. P. Gromov, A. V. Buevich, I. I. Baskin, O. A. Fedorova, A. I. Vedernikov, M. V. Alfimov, B. Eliasson and U. Edlund, Crown-containing styryl dyes: Cation-induced self-assembly of multiphotochromic 15-crown-5 ethers into photoswitchable molecular devices, J. Chem. Soc., Perkin Trans. 2, 1999, 601.

    Google Scholar 

  26. A. I. Vedernikov and S. P. Gromov, Convenient method for the preparation of crown ether cinnamaldehydes, Synthesis, 2001, 889.

    Google Scholar 

  27. S. P. Gromov, A. I. Vedernikov, E. N. Ushakov, L. G. Kuz’mina, A. V. Feofanov, V. G. Avakyan, A. V. Churakov, Yu. S. Alaverdyan, E. V. Malysheva, M. V. Alfimov, J. A. K. Howard, B. Eliasson and U. G. Edlund, Synthesis, structure, spectroscopic studies, and complexation of novel crown ether butadienyl dyes, Helv. Chim. Acta, 2002, 85, 60.

    Article  CAS  Google Scholar 

  28. H-type dye aggregation commonly results in absorption band splitting; in many cases, the weaker, lower-energy band is unresolved and reveals itself as a shoulder of the more intense, higher-energy band: (a) V. I. Yuzhakov, Association of dye molecules and its spectroscopic manifestation, Russ. Chem. Rev., 1979, 48, 1076

    Article  Google Scholar 

  29. E. N. Ushakov, S. P. Gromov, O. A. Fedorova and M. V. Alfimov, Crown-containing styryl dyes. 19. Complexation and cation-induced aggregation of chromogenic aza-15-crown-5 ethers, Russ. Chem. Bull., 1997, 46, 463.

    Article  CAS  Google Scholar 

  30. The set of experimental spectra shown in Fig. 1 was reconstructed within a residual error of 0.0012 optical density units by a factor analysis method under the assumption that there areonly two absorbing components in the system; the small value of residual error suggests that contribution from a third component to the total spectral variation can be neglected: (a) J. J. Kankare, Computation of equilibrium constants for multicomponent systems from spectrophotometric data, Anal. Chem., 1970, 42, 1322

    Article  CAS  Google Scholar 

  31. E. N. Ushakov, S. P. Gromov, O. A. Fedorova, Yu. V. Pershina, M. V. Alfimov, F. Barigelletti, L. Flamigni and V. Balzani, Sandwich-type complexes of alkaline-earth metal cations with a bisstyryl dye containing two crown ether units, J. Phys. Chem. A, 1999, 103, 11188.

    Article  CAS  Google Scholar 

  32. MeCN solutions of dye 5 and complex (5⊙Mg2+)2 were prepared in a darkroom under red light. Spectral experiments were conducted in quartz cells with ground stoppers to avoid MeCN evaporation during the experiments. The atmospheric oxygen contained in solutions was not removed. Luminescence spectra were corrected taking into account the spectral sensitivity of the photomultiplier tube. Luminescence quantum yields jlum were determined using [Ru(bpy)3]Cl2 in air-equilibrated water as the reference compound. The jlum value for the reference is 0.028: K. Nakamaru, Synthesis, luminescence quantum yields, and lifetimes of trischelated ruthenium (II) mixed-ligand complexes including 3,3-dimethyl-2,2-bipyridyl, Bull. Chem. Soc. Jpn., 1982, 55, 2697.

    Article  CAS  Google Scholar 

  33. The signals from cyclobutane protons H(c) and H(d) are overlapped by an intense signal from the protons of CH2O groups.

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Authors and Affiliations

  1. Department of Nanophotonics, Institute of Problems of Chemical Physics, Chernogolovka, 142432, Moscow Region, Russia

    Evgeny N. Ushakov

  2. Photochemistry Centre, Novatorov str. 7A-1, Moscow, 119421, Russia

    Artem I. Vedernikov, Michael V. Alfimov & Sergey P. Gromov

Authors
  1. Evgeny N. Ushakov
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  2. Artem I. Vedernikov
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  3. Michael V. Alfimov
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  4. Sergey P. Gromov
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Corresponding authors

Correspondence to Evgeny N. Ushakov or Sergey P. Gromov.

Additional information

† Electronic supplementary information (ESI) available: Absorption spec-troscopy data for a cationic analogue of dye 5; global analysis of spectrophotometric titration data (factor analysis, discussion on com-plexation stoichiometry, parameterized modelling of absorption spectra); molecular mechanics and DFT modelling of dimers (5⊙Mg2+)2. See DOI: 10.1039/c0pp00227e

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Ushakov, E.N., Vedernikov, A.I., Alfimov, M.V. et al. Regio- and stereospecific [2+2] photocyclodimerization of a crown-contain butadienyl dye via cation-induced self-assembly in solution. Photochem Photobiol Sci 10, 15–18 (2011). https://doi.org/10.1039/c0pp00227e

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  • DOI: https://doi.org/10.1039/c0pp00227e

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