Abstract
With the aim of controlling free space available for the reactants, photochemical reactivity of several 4-alkyl dibenzyl ketones included within a water-soluble self-assembled organic capsule (octa acid) has been investigated. One and two-dimensional NMR spectroscopic techniques were employed to characterize the structure of the guest@host complexes. Free space controlled by the remote alkyl group influences the distribution of photoproducts. Correlation between the structures of the guest@host complexes and products selectivity suggested that the free space that could be controlled by a remote tether has a determining role during a photoreaction within the restricted space of the capsule. The fact that the same alkyl tether has no effect on the photobehavior of 4-alkyl dibenzyl ketones in hexane solution suggests that the role of substituents in free (solution) and restricted space (supramolecular assemblies) is different. The current observation suggests that rules of physical organic chemistry and photochemistry developed based on solution chemistry cannot be simply extended to supramolecular assemblies.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
R. G. Weiss, V. Ramamurthy and G. S. Hammond, Acc. Chem. Res., 1993, 26, 530–536.
V. Ramamurthy, R. G. Weiss and G. S. Hammond, Adv. Photochem., 1993, 18, 67–236.
N. J. Turro, and M. A. Garcia-Garibay, in Photochemistry in Organized & Constrained Media, ed. V. Ramamurthy, VCH Publishers, New York, 1991, pp. 1–38.
M. D. Cohen, Angew. Chem., Int. ed. Engl., 1975, 14, 386–393.
N. J. Turro, Proc. Nat. Acad. Sci. USA, 2005, 102, 10766–10770.
P. S. Engel, J. Am. Chem. Soc., 1970, 92, 6074–6076.
W. K. Robbins and R. H. Eastman, J. Am. Chem. Soc., 1970, 92, 6076–6077.
C. L. D. Gibb and B. C. Gibb, J. Am. Chem. Soc., 2004, 126, 11408–11409.
M. V. S. N. Maddipatla, L. S. Kaanumalle, A. Natarajan, M. Pattabiraman and V. Ramamurthy, Langmuir, 2007, 23, 7545–7554.
M. Pattabiraman, A. Natarajan, L. S. Kaanumalle and V. Ramamurthy, Org. Lett., 2005, 7, 529–532.
M. Pattabiraman, A. Natarajan, R. Kaliappan, J. T. Mague and V. Ramamurthy, Chem. Commun., 2005, 4542–4544.
M. Pattabiraman, L. S. Kaanumalle, A. Natarajan and V. Ramamurthy, Langmuir, 2006, 22, 7605–7609.
R. Kaliappan, M. V. S. N. Maddipatla, L. S. Kaanumalle and V. Ramamurthy, Photochem. Photobiol. Sci., 2007, 6, 737–740.
R. Kaliappan, L. S. Kaanumalle, A. Natarajan and V. Ramamurthy, Photochem. Photobiol. Sci., 2006, 5, 925–930.
R. Kaliappan, L. S. Kaanumalle and V. Ramamurthy, Chem. Commun., 2005, 4056–4058.
S. Karthikeyan and V. Ramamurthy, J. Org. Chem., 2006, 71, 6409–6413.
S. Karthikeyan and V. Ramamurthy, J. Org. Chem., 2007, 72, 452–458.
L. S. Kaanumalle, R. Ramesh, V. S. N. MurthyMaddipatla, J. Nithyanandhan, N. Jayaraman and V. Ramamurthy, J. Org. Chem., 2005, 70, 5062–5069.
L. S. Kaanumalle, J. Nithyanandhan, M. Pattabiraman, N. Jayaraman and V. Ramamurthy, J. Am. Chem. Soc., 2004, 126, 8999–9006.
M. Pattabiraman, L. S. Kaanumalle and V. Ramamurthy, Langmuir, 2006, 22, 2185–2192.
M. M. Conn and J. Rebek, Chem. Rev., 1997, 97, 1647–1668.
L. Arne, Angew. Chem., Int. Ed., 2005, 44, 1000–1002.
F. Corbellini, R. M. A. Knegtel, P. D. J. Grootenhuis, M. Crego-Calama and D. N. Reinhoudt, Chem.-Eur. J., 2005, 11, 298–307.
N. J. Turro and W. R. Cherry, J. Am. Chem. Soc., 1978, 100, 7431–7432.
N. J. Turro and B. Kraeutler, Acc. Chem. Res., 1980, 13, 369–377.
B. N. Rao, N. J. Turro and V. Ramamurthy, J. Org. Chem., 1986, 51, 460–464.
B. N. Rao, M. S. Syamala, N. J. Turro and V. Ramamurthy, J. Org. Chem., 1987, 52, 5517–5521.
S. S. Petrova, A. I. Kruppa and T. V. Leshina, Chem. Phys. Lett., 2004, 385, 40–44.
N. J. Turro and P. Wan, J. Am. Chem. Soc., 1985, 107, 678–682.
M. A. Garcia-Garibay, Z. Zhang and N. J. Turro, J. Am. Chem. Soc., 1991, 113, 6212–6218.
M. Warrier, L. S. Kaanumalle and V. Ramamurthy, Can. J. Chem., 2003, 81, 620–631.
U. Bhattacharjee, C. A. Chesta and R. G. Weiss, Photochem. Photobiol. Sci., 2004, 3, 287–295.
C. A. Chesta, J. Mohanty, W. M. Nau, U. Bhattacharjee and R. G. Weiss, J. Am. Chem. Soc., 2007, 129, 5012–5022.
L. S. Kaanumalle, C. L. D. Gibb, B. C. Gibb and V. Ramamurthy, J. Am. Chem. Soc., 2004, 126, 14366–14367.
A. K. Sundaresan and V. Ramamurthy, Org. Lett., 2007, 9, 3575–3578.
D. J. Cram, and J. M. Cram, Container Molecules and Their Guests, The Royal Society of Chemistry, Cambridge, 1994.
A. Jasat and J. C. Sherman, Chem. Rev., 1999, 99, 931–968.
A. Natarajan, L. S. Kaanumalle, S. Jockusch, C. L. D. Gibb, B. C. Gibb, N. J. Turro and V. Ramamurthy, J. Am. Chem. Soc., 2007, 129, 4132–4133.
C. L. D. Gibb, A. K. Sundaresan, V. Ramamurthy and B. C. Gibb, J. Am. Chem. Soc., 2008, 130, 4069–4080.
L. Lunazzi, K. U. Ingold and J. C. Scaiano, J. Phys. Chem., 1983, 87, 529–530.
N. J. Turro, I. R. Gould and G. H. Bartez, J. Phys. Chem., 1983, 87, 531–532.
S. Mecozzi and J. Rebek, Jr., Chem.-Eur. J., 1998, 4, 1016–1022.
Author information
Authors and Affiliations
Additional information
This paper was published as part of the themed issue in honour of Nicholas Turro.
Electronic supplementary information (ESI) available: Experimental details and NMR spectra of the complexes. See DOI: 10.1039/b814001d
Rights and permissions
About this article
Cite this article
Sundaresan, A.K., Ramamurthy, V. Consequences of controlling free space within a reaction cavity with a remote alkyl group: photochemistry of para-alkyl dibenzyl ketones within an organic capsule in water. Photochem Photobiol Sci 7, 1555–1564 (2008). https://doi.org/10.1039/b814001d
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/b814001d