Abstract
2-Styrylbenzothiazole (1) and cinnamic acid (2) derivatives containing 15-crown-5 ether moieties form a supramolecular assembly in the presence of Ba2+ cations in acetonitrile. The assembly is stabilized by hydrogen bonding between the heterocyclic N atom of 1 and the proton of the carboxylic group of 2, by sandwich Ba2+ complex formation between the crown ether moieties of 1 and 2, and by p–p stacking interactions. Irradiation of solutions containing these supramolecular complexes leads to highly specific formation of an unsymmetrical cycloadduct. This investigation provides an interesting example of supramolecular control of [2 + 2]-photocyclization in solution.
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F. Bernardi, M. Olivucci, and M. A. Robb, Predicting forbidden and allowed cycloaddition reactions: potential surface topology and its rationalization, Acc. Chem. Res., 1990, 23, 405–412.
For reviews, see J. Saltiel and J. L. Charlton, Cis-trans isomerization of olefins in Rearrangements in Ground and Excited States, ed. P. de Mayo, 1980, vol. III, pp. 25–89.
J. Saltiel and Y.-P. Sun, Cis-trans isomerization of C,C double bonds, in Photochromism, Molecules and Systems, ed. H. Dürr and H. Bouas-Laurent, Elsevier, Amsterdam, 1990, pp. 64–164.
F. Müller, and J. Mattay, Photocycloadditions: Control by energy and electron transfer, Chem. Rev., 1993, 93, 99–117.
R. A. Caldwell, K. Mizuno, P. E. Hansen, L. P. Vo, M. Frentrup, and C. D. Ho, Photochemistry of the phenanthrene-stilbene system. Cycloaddition and singlet-sensitized isomerization, J. Am. Chem. Soc., 1981, 103, 7263–7269.
W. K. Smothers, M. C. Meyer, and J. Saltiel, Photocycloaddition of 9,10-dichloroanthracene to 1,3-cyclohexadiene, J. Am. Chem. Soc., 1983, 105, 545–555.
J. L. R. Williams, J. M. Carlson, G. A. Teynolds, and R. E. Adel, Photodimers of 4’-substituted 2-styrylpyridines, J. Org. Chem., 1963, 28, 1317–1320.
M. Horner, and S. Hunig, Pyridylsubstituierte Cyclobutane durch Photodimerisierung von Azastilbenen, Liebigs Ann. Chem., 1982, 6, 1183–1192.
W. Zhang, G. Shen, J. Zhuang, P. Zheng, and X. Ran, Synthesis and photolysis of r-1,c-2,t-3,t-4-1,3-di(4-R-phenyl)-2,4-bis[2-(5-phenyloxazolyl)]cyclobutane, Photochem. Photobiol., A, 2002, 147, 25–30.
D. Donati, M. Fiorenza, P. Sarti-Fantoni, Photochemical reactions of 3-methyl-4-nitro-5-styrylisoxazole in solution, in the solid state, and adsorbed on silica gel, J. Heterocycl. Chem., 1979, 16, 253–256.
W. Q. Zhang, J. P. Zhuang, C. B. Li, H. Sun, and X. N. Yuan, Structure and photochemical properties of r-1,c-2,t-3,t-4-1,3-bis[2-(5-R-benzoxazolyl)]-2,4-di(4-R’-phenyl) cyclobutane, Chinese J. Chem., 2001, 19, 695–701.
O. A. Fedorova, Y. V. Fedorov, A. I. Vedernikov, S. P. Gromov, O. V. Yescheulova, M. V. Alfimov, M. Woerner, S. Bossmann, A. Braun, and J. Saltiel, Thiacrown ether substituted styryl dyes: synthesis, complex formation and multiphotochromic properties, J. Phys. Chem. A, 2002, 106, 6213–6222.
E. N. Ushakov, S. P. Gromov, A. V. Buevich, I. I. Baskin, O. A. Fedorova, A. 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 device, J. Chem. Soc., Perkin Trans. 2, 1999, 601–607.
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, 6115–6125.
S. P. Gromov, O. A. Fedorova, E. N. Ushakov, A. V. Buevich, I. I. Baskin, Y. V. Pershina, B. Eliasson, U. Edlund, and M. V. Alfimov, Photoswitchable molecular pincers: synthesis, self-assembly into sandwich complexes and ion-selective intramolecular [2 + 2]-photocycloaddition of an unsaturated bis-15-crown-5 ether, J. Chem. Soc., Perkin Trans. 2, 1999, 1323–1329.
J. H. Kim, Y. Tani, M. Matsuoka, and K. Fukunishi, Topochemical photoreaction of self-assembled styryldicyanopyrazine dyes and their solid state spectral properties, Dyes Pigments, 1999, 43, 7–14.
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., 2003, 115, 1158–1164.
Yu. Fedorov, O. Fedorova, N. Schepel, S. Gromov, M. Alfimov, A. M. Turek, and J. Saltiel, Synthesis and multitopic complex formation of a photochromic bis(crownether) based on benzobis(thiazole), J. Phys. Chem., 2005, 109, 8653–8660.
M. Pattabiraman, A. Natarajan, R. Kaliappan, J. T. Mague, and V. Ramamurthy, Template directed photodimerization of trans-1,2-bis(n-pyridyl)ethylenes and stilbazoles in water, Chem. Commun., 2005, 4542–4544.
V. Darcos, K. Grirth, X. Sallenave, J.-P. Desvergne, C. Guyard-Duhayon, B. Hasenknopf, and D. M. Bassani, Supramolecular control of [2 + 2] photodimerization via hydrogen bonding, Photochem. Photobiol. Sci., 2003, 2, 1152–1161.
Y. V. Pol, R. Suau, E. Perez-Inestrosa, and D. M. Bassani, Synergistic effects in controlling excited-state photodimerisation using multiple supramolecular interactions, Chem. Commun., 2004, 1270–1271.
T. Friscic, and L. R. MacGillivray, Reversing the code of a template-directed solid-state synthesis: a bipyridine template that directs a single-crystal-to-single-crystal [2 + 2]-photodimerisation of a dicarboxylic acid, Chem. Commun., 2005, 5748–5750.
T. Friscic, D. M. Drab, and L. R. MacGillivray, A test for homology: photoactive crystalline assemblies involving linear templates based on a homologous series of phloroglucinols, Org. Lett., 2004, 6, 4647–4650.
G. S. Papaefstathiou, I. G. Georgiev, T. Friscic, and L. R. MacGillivray, Directed assembly and reactivity of olefins within a one-dimensional ladder-like coordination polymer based on a dinuclear Zn(ii) platform, Chem. Commun., 2005, 3974–3976.
O. A. Fedorova, E. N. Andryukhina, and S. P. Gromov, Facile synthesis of novel 2-styrylbenzothiazoles containing crown ether moieties, Synthesis, 2003, 371–374.
M. Shirai, T. Orikata, and M. Tanaka, Cation binding properties of poly(crown ethers) with photodimerizable groups, J. Polym. Sci.: Polym. Chem. Ed., 1985, 23, 463–477.
S. P. Gromov, A. V. Vedernikov, Yu. V. Fedorov, O. A. Fedorova, E. N. Andryukhina, N. E. Shepel, M. V. Alfimov, and J. Saltiel, Self-assembly into sandwich complex and stereoselective [2 + 2]-photocycloaddition of crown-containing benzothiazolylphenylethene, Russ. Chem. Bull., 2005, 54, 1524–1533.
P. Gans, A. Sabatini, and A. Vacca, Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs, Talanta, 1996, 43, 1739–1753.
G. Giamician, and P. Silber, Chemische Lichtwirkungen, Ber., 1903, 36, 4266–4272.
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Fedorova, O., Fedorov, Y.V., Gulakova, E. et al. Supramolecular photochemical synthesis of an unsymmetrical cyclobutane. Photochem Photobiol Sci 6, 1097–1105 (2007). https://doi.org/10.1039/b707093d
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DOI: https://doi.org/10.1039/b707093d