Abstract
A simple strategy that is based on conversion of an electron-rich pyridyl to an electron-deficient pyridinium ion is able to orient thirteen of the sixteen olefins investigated towards a single dimer in quantitative yield in the crystalline state. The reagent used is HCl, the method involves grinding the olefin with a drop of HCl and the dimerization is achieved by exposure of the crystalline stilbazolium·HCl salts to light. The weak force involved in modifying the crystal packing is most likely charge-transfer interaction.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Notes and references
G. M. J. Schmidt, et al., Solid State Photochemistry, Verlag Chemie, New York, 1976.
Y. Ito, B. Borecka, G. Olovsson, J. Trotter and J. R. Scheffer, Control of the Solid-state photodimerization of some derivatives and analogs of trans-cinnamic acid by ethylenediamine, Tetrahedron Lett., 1995, 36, 6087–6090.
Y. Ito, B. Borecka, J. Trotter and J. R. Scheffer, Control of solid-state photodimerization of trans-cinnamic acid by doule salt formation with diamines, Tetrahedron Lett., 1995, 36, 6083–6086.
Y. Ito, H. Hosomi and S. Ohba, Compelled Orientational Control of the Solid-State Photodimerization of trans-Cinnamamides: Dicar-boxylic Acid as a Non-covalent Linker, Tetrahedron, 2000, 56, 6833–6844.
K. Tanaka and T. Fujiwara, Enantioselective [2 + 2] Photodimerization Reactions of Coumarins in Solution, Org. Lett., 2005, 7, 1501–1503.
K. Tanaka, E. Mochizuki, N. Yasui, Y. Kai, I. Miyahara, K. Hirotsu and F. Toda, Single-Crystal-to Single-Crystal Enantioselective [2 + 2] Photodimerization of Coumarin, Thiocoumarin and Cyclohex-2-enone in the Inclusion Complexes with Chiral Host Compounds, Tetrahedron, 2000, 56, 6853–6865.
L. R. MacGillivray, G. S. Papaefstathiou, T. Friscic, T. D. Hamilton, D.-K. Bucar, Q. Chu, D. B. Varshney and I. G. Georgiev, Supramolecular control of Reactivity in the Solid State: From Templates to Ladderanes to Metal–Organic Frameworks, Acc. Chem. Res., 2008, 41, 280–291.
M. Nagarathinam, A. M. P. Peedikakkal and J. J. Vittal, Stacking of double bonds for photochemical [2 + 2] cycloaddition reactions in the soild state, Chem. Commun., 2008, 5277–5288.
M. Pattabiraman, A. Natarajan, R. Kaliappan, J. T. Mague and V. Ramamuthy, Template directed photodimerization of trans-1,2-bis(n-pyridyl)-ethylenes and stilbazoles in water, Chem. Commun., 2005, 4542–4544.
M. V. S. N. Maddipatla, L. S. Kaanumalle, A. Natarajan, M. Pattabiraman and V. Ramamurthy, Preorientation of Olefins toward a Single Photodimer: Cucurbituril-Mediated Photodimerization of Protonated Azastilbenes in Water, Langmuir, 2007, 23, 7545–7554.
R. Kaliappan, L. S. Kaanumalle, A. Natarajan and V. Ramamuthy, Templating photodimerization of stilbazoles with water-soluble cal-ixarenes, Photochem. Photobiol. Sci., 2006, 5, 925–930.
R. Kaliappan, M. V. S. N. Maddipatla, L. S. Kaanumalle and V. Ramamurthy, Crystal engineering principles applied to solution photochemistry: controlling the photodimerization of stilbazolium salts within γ-cyclodextrin and cucurbit[8]uril in water, Photochem. Photobiol. Sci., 2007, 6, 737–740.
B. R. Bhogala, B. Captain, A. Parthasararthy and V. Ramamurthy, Thiourea as a Template for Photodimerization of Azastilbenes, J. A m. Chem. Soc., 2010, 132, 13434–13442.
J. L. R. Williams, Photodimerization of 2-Styrylpyridine, J. Org. Chem., 1960, 25, 1839–1840.
J. L. R. Williams, J. M. Carlson, G. A. Reynolds and R. E. Adel, Photodimers of 4′-Substituted 2-Styrylpyridines, J. Org. Chem., 1963, 28, 1317–1320.
J. L. R. Williams, S. K. Webster and J. A. V. Allan, cis and trans Isomers of 2-Styrylpyridine, J. Org. Chem., 1961, 26, 4893–4895.
F. H. Quina and D. G. Whitten, Medium Effects on Photochemical Reactions. Photochemistry of Surfactant Alkyl-4-stilbazole Salts in solution, in the Solid State, and in Monolayer Assemblies, J. Am. Chem. Soc., 1975, 97, 1602–1603.
M. Horner and S. Hunig, Bicyclo[1.1.0]butanes. A New Synthetic Route and Valence Isomerizations, J. Am. Chem. Soc., 1977, 99, 6120–6122.
F. H. Quina and D. G. Whitten, Photochemical Reactions in Organized Monolayer Assemlies. 4. Photodimerization, Photoisomerization, and Excimer Formation with Surfactant Olefins and Dienes in Monolayer Assemblies, Crystals, and Micelles, J. Am. Chem. Soc., 1977, 99, 877–883.
S. Yamada, N. Uematsu and K. Yamashita, Role of Cation -π Interaction in the Photodimerization of trans-4-Styrylpyridines, J. A m. Chem. Soc., 2007, 129, 12100–12101.
X.-H. Li, L.-Z. Wu, L.-P. Zang and C.-H. Tung, Controlled Photocyclization, Photodimerization, and Photoisomerization of Stilbazole Salts within Nafion Membranes, Org. Lett., 2002, 4, 1175–1177.
D. G. Whitten and Y. J. Lee, Photoaddition and Photoreduction Reactions of Azastilbenenes. Solvent Effects on the Photoreactivity of Aza Aromatics, J. Am. Chem. Soc., 1972, 94, 9142–9148.
D. G. Whitten and M. T. McCall, Radiationless Processes in the Photochemistry of Stilbazoles and 1,2-Bispyridylethylenes, J. Am. Chem. Soc., 1969, 91, 5097–5103.
V. Ramamurthy and K. Venkatesan, Photochemical Reactions of Organic Crystals, Chem. Rev., 1987, 87, 433–481.
K. B. Yoon, Electron- and Charge-Transfer Reactions within Zeolites, Chem. Rev., 1993, 93, 321–339.
Author information
Authors and Affiliations
Corresponding author
Additional information
Electronic supplementary information (ESI) available: Experimental procedures. CCDC reference numbers 813287–813301. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1pp05070b
Rights and permissions
About this article
Cite this article
Mondal, B., Captain, B. & Ramamurthy, V. Photodimerization of HCl salts of azastilbenes in the solid state. Photochem Photobiol Sci 10, 891–894 (2011). https://doi.org/10.1039/c1pp05070b
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/c1pp05070b