Abstract
(1E,3E)-1,4-Diphenylbuta-1,3-diene is photostable in the crystalline state, while fluoro-substitution induces reactivity. Crystals of (1E,3E)-1-pentafluorophenyl-4-(4-methoxyphenyl)buta-1,3-diene 1, (1E,3E)-1-pentafluorophenyl-4-(4-methylphenyl)buta-1,3-diene 2 and (1E,3E)-1-pentafluorophenyl-4-phenylbuta-1,3-diene 3 undergo double [2+2] photodimerization topochemically to yield anti head-to-tail photodimers in the crystalline state. Remarkably fluoro-substitution brings the reactant molecules into an anti head-to-tail arrangement in the crystal lattice with weak intermolecular interactions: C-HρρρF, FρρρF, C-Hρρρπ, πρρρπ.
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References
M. D. Cohen, G. M. J. Schmidt, Topochemistry. Part I. A Survey, J. Chem. Soc., 1964, 1996–2000.
M. D. Cohen, G. M. J. Schmidt and F. I. Sonntag, Topochemistry. Part II. The photochemistry of trans-cinnamic acids, J. Chem. Soc., 1964, 2000–2013.
G. M. J. Schmidt, Topochemistry. Part III. The crystal chemistry of some trans-cinnamic acids, J. Chem. Soc., 1964, 2014–2021.
V. Ramamurthy and K. Venkatesan, Photochemical reactions of organic crystals, Chem. Rev., 1987, 87, 433–481.
K. Venkatesan and V. Ramamurthy, Photochemistry in Organized and Constrained Media, ed. V. Ramamurthy, Ch. 4, p. 133, VCH, New York, 1991.
G. R. Desiraju, Crystal Engineering: The Design of Organic Solids, Elsevier, Amsterdam, 1989.
P. Venugopalan, T. Bharati Rao and K. Venkatesan, Studies in crystal engineering: Photochemical and crystallographic investigations of bromocoumarins and (±)-7-(p-bromobenzylidene)piperitone, J. Chem. Soc., Perkin Trans. 2, 1991, 981–987.
K. Gnanaguru, N. Ramasubbu, K. Venkatesan and V. Ramamurthy, A study on the photochemical dimerization of coumarins in the solid state, J. Org. Chem., 1985, 50, 2337–2346.
N. Ramasubbu, K. Gnanaguru, K. Venkatesan and V. Ramamurthy, Topochemical photodimerization of 7-acetoxycoumarin: The acetoxy group as a steering agent, Can. J. Chem., 1982, 60, 2159–2161.
K. Vishnumurthy, T. N. Guru Row and K. Venkatesan, Studies in crystal engineering: effect of fluorine substitution in crystal packing and topological photodimerization of styrylcoumarins in the solid state, J. Chem. Soc., Perkin Trans. 2, 1996, 1475–1478.
K. Vishnumurthy, T. N. Guru Row and K. Venkatesan, Studies in crystal engineering: Steering ability of fluorine in 4-styrylcoumarins, Tetrahedron, 1999, 55, 4095–4108.
K. Vishnumurthy, T. N. Guru Row and K. Venkatesan, Unusual photodimerization of 7-fluoro-4-methylcoumarin and 6-fluoro-4-methylcoumarin in the solid state, Tetrahedron, 1998, 54, 11235–11246.
V. Amarendra Kumar, N. S. Begum and K. Venkatesan, Crystal engineering: Fluorine as a new steering group, J. Chem. Soc., Perkin Trans. 2, 1993, 463–467.
J. Narasimha Moorthy and K. Venkatesan, Photobehavior of crystalline 4-styrylcoumarin dimorphs: Structure-reactivity correlations, Bull. Chem. Soc. Jpn., 1994, 67, 1–6.
V. Amarendra Kumar and K. Venkatesan, Studies in crystal engineering: Topochemical photodimerization of (±)-p-fluorobenzylidenepiperitone, J. Chem. Soc., Perkin Trans. 2, 1993, 2429–2433.
P. Venugopalan and K. Venkatesan, Solid state photobehaviour and crystal packing of o-chlorobenzylidene-DL-piperitone: Influence of molecular topology on photobehaviour, Acta Crystallogr., Sect. B: Struct. Sci., 1992, 48, 532–537.
H. Hopf, H. Greiving, P. G. Jones and P. Bubenitschek, Topochemcial reaction control in solution, Angew. Chem., Int. Ed. Engl., 1995, 34, 685–687.
M. Hasegawa, M. Nohara, K. Saigo, T. Mori and H. Nakanishi, Photodimerization of 1,4-dicinnamoylbenzene crystal via a topochemical process, Tetrahedron Lett., 1984, 25, 561–564.
M. Hasegawa, K. Saigo, T. Mori, H. Uno, M. Nohara and H. Nakanishi, Topochemical “double” photodimerization of the 1,4-dicinnamoylbenzene crystal, J. Am. Chem. Soc., 1985, 107, 2788–2793.
Y. Shen and T. Wang, Highly stereoselective synthesis of substituted 1-pentafluorophenylbuta-1,3-dienes, J. Fluorine Chem., 1997, 82, 139–141.
Y. Shen and T. Wang, One-pot synthesis of 1-pentafluorophenyl-1,3-butadienes, J. Fluorine Chem., 1994, 67, 33–35.
G. S. Murthy, P. Arjunan, K. Venkatesan and V. Ramamurthy, Consequences of lattice relaxability in solid state photodimerizations, Tetrahedron, 1987, 43, 1225–1240.
A. Bondi, van der Waals volumes and radii, J. Phys. Chem., 1964, 68, 441–451.
P. Murray-Rust, W. C. Stallings, C. T. Monti, R. K. Preston and J. P. Glusker, Intermolecular interactions of the C-F bond: The crystallographic environment of fluorinated carboxylic acids and related structures, J. Am. Chem. Soc., 1983, 105, 3206–3214.
C. F. Castano, C. F. Foces, F. H. Cano, R. M. Claramunt, C. Escolatico, A. Fruchier and J. Elguero, The structure, conformation and molecular packing of pyrazolyl fluorobenzene and their inclusion compounds, New J. Chem., 1997, 21, 195–213.
L. Shimoni and J. P. Glusker, The geometry of intermolecular interaction in some crystalline fluorine-containing organic compounds, Struct. Chem., 1994, 5, 383–397.
L. Shimoni, J. P. Glusker and C. W. Bock, Structures and dissociation energies of the complexes CHmFn?NH4+ (n + m = 4, n = 1-3): An ab initio molecular orbital study, J. Phys. Chem., 1995, 99, 1194–1198.
J. A. K. Howard, V. J. Hoy, D. O’Hagan and G. T. Smith, How good is fluorine as a hydrogen bond acceptor?, Tetrahedron, 1996, 52, 12613–12622.
J. D. Dunitz and R. Taylor, Organic fluorine hardly ever accepts hydrogen bonds, Chem. Eur. J., 1997, 3, 89–98.
J. D. Dunitz, Weak intermolecular interactions in solids, liquids, Mol. Cryst. Liq. Cryst., 1996, 279, 209–218.
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Vishnumurthy, K., Guru Row, T.N. & Venkatesan, K. Fluorine in crystal engineering: photodimerization of (1E,3E)-1- phenyl-4-pentafluorophenylbuta-1,3-dienes in the crystalline state. Photochem Photobiol Sci 1, 427–430 (2002). https://doi.org/10.1039/b202557d
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DOI: https://doi.org/10.1039/b202557d