Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
REVIEW

Electrochemistry of Redox Active Centres Encapsulated by Non-Covalent Methods

Suresh Gadde A , Elizabeth K. Batchelor A and Angel E. Kaifer A B
+ Author Affiliations
- Author Affiliations

A Center for Supramolecular Science and Department of Chemistry, University of Miami, Coral Gables, FL 33124-0431, USA.

B Corresponding author. Email: akaifer@miami.edu




Suresh Gadde was born in Vinukonda, Andhra Pradesh, India. He received a M.Sc. from University of Hyderbad, Hyderbad, India in 2000, and completed his Ph.D. from Wichita State University (with Professor Francis D’Souza) in 2006. Currently, he is a post-doctoral fellow at the University of Miami with Professor A. E. Kaifer. His research interests involve photo- and electrochemical studies on supramolecular systems.



Elizabeth K. Batchelor was born in West Palm Beach, Florida, USA. She received her B.Sc. in Chemistry from the University of Miami in 2009, and is currently pursuing a M.Sc. in Chemistry at the University of Texas at Austin before continuing on to medical school. She is always excited about any chemistry, especially when it involves pretty colours (dyes or charge transfer complexes).



Angel E. Kaifer was born in Madrid, Spain, where he completed his undergraduate studies in chemistry at Universidad Autónoma. He earned his Ph.D. (with Luis Echegoyen) in 1984 at the University of Puerto Rico, Rio Piedras, and did postdoctoral work (with Allen Bard) at the University of Texas, Austin. In 1985, he joined the faculty of the University of Miami, where he is now Professor of Chemistry. His research interests focus on the electrochemistry of supramolecular systems, with current emphasis on functionalized dendrimers, molecular capsules, hydrogen-bonded systems, and the binding properties of cucurbit[n]uril hosts.

Australian Journal of Chemistry 63(2) 184-194 https://doi.org/10.1071/CH09390
Submitted: 18 July 2009  Accepted: 20 October 2009   Published: 26 February 2010

Abstract

This manuscript presents a summary of recent research work on the electrochemical behaviour of redox active guests fully or almost fully encapsulated by suitable molecular receptors or molecular capsules. From the standpoint of their voltammetric behaviour the cyclodextrins have been shown to be very dynamic hosts, which hamper the observation of direct electron transfer to/from their inclusion complexes. Therefore, this Review is essentially concerned with research work on cucurbituril and cavitand-type hosts, which was mostly done in the author’s laboratory. In general terms, the observed voltammetric behaviour for encapsulated guests covers a wide range of possibilities. Cucurbituril and cavitand-type hosts afford more kinetically stable complexes, whose direct electrochemical behaviour is observable and tends to be kinetically slower than that of the free guests. However, the degree of kinetic attenuation varies over a wide range and, in some cases, challenges our ability to rationalize the data. Clearly, more variation in the host structures and more research work are required to improve our understanding of encapsulation effects on these electron transfer reactions.


Acknowledgements

The authors are grateful to the USA National Science Foundation for continued support of this research work. A.K. wishes to acknowledge the many contributions by members of his research group, whose names are listed in the corresponding publications.


References


[1]   S. M. Biros, J. Rebek, Chem. Soc. Rev. 2007, 36,  93.
        | CrossRef |   

[2]   A. Lützen, Angew. Chem. Int. Ed. 2005, 44,  1000.
        | CrossRef |   

[3]   M. R. Johnston, M. J. Latter, J. Supramol. Chem. 2005, 17,  595.
        | CrossRef |   

[4]   J. Rebek, Angew. Chem. Int. Ed. 2005, 44,  2068.
        | CrossRef |   

[5]   D. M. Vriezema, M. C. Aragones, J. A. A. W. Elemans, J. J. L. M. Cornelissen, A. E. Rowan, R. J. M. Nolte, Chem. Rev. 2005, 105,  1445.
        | CrossRef |   

[6]   J. L. Atwood, L. J. Barbour, A. Jerga, Perspect. Supramol. Chem. 2003, 7,  153.
        | CrossRef |   

[7]   B. C. Gorman, J. C. Smith, Acc. Chem. Res. 2001, 34,  60.
        | CrossRef |   

[8]   K. A. Connors, Chem. Rev. 1997, 97,  1325.
        | CrossRef |   

[9]   J. Szejtli, Chem. Rev. 1998, 98,  1743.
        | CrossRef |   

[10]   M. V. Rekharsky, Y. Inoue, Chem. Rev. 1998, 98,  1875.
        | CrossRef |   

[11]   J. W. Lee, S. Samal, N. Selvapalam, H.-J. Kim, K. Kim, Acc. Chem. Res. 2003, 36,  621.
        | CrossRef |   

[12]   J. Lagona, P. Mikhopadhyay, S. Chakrabartri, L. Isaacs, Angew. Chem. Int. Ed. 2005, 44,  4844.
        | CrossRef |   

[13]   Y. H. Ko, E. Kim, I. Hwang, K. Kim, Chem. Commun. 2007,  1305.
        | CrossRef |   

[14]   L. Isaacs, Chem. Commun. 2009,  619.
        | CrossRef |   

[15]   M. V. Rekharsky, T. Mori, C. Yang, Y. H. Ko, N. Selvapalam, H. Kim, D. Sobransingh, A. E. Kaifer, S. Liu, L. Isaacs, W. Chen, S. Moghaddam, M. K. Gilson, K. Kim, Y. Inoue, Proc. Natl. Acad. Sci. USA 2007, 104,  20737.
        | CrossRef |   

[16]   W. S. Jeon, K. Moon, S. H. Park, H. Chun, Y. H. Ko, J. Y. Lee, E. S. Lee, S. Samal, N. Selvapalam, M. V. Rekharsky, V. Sindelar, D. Sobransingh, Y. Inoue, A. E. Kaifer, K. Kim, J. Am. Chem. Soc. 2005, 127,  12984.
        | CrossRef |   

[17]   A. R. Khan, P. Forgo, K. J. Stine, V. T. D’Souza, Chem. Rev. 1998, 98,  1977.
        | CrossRef |   

[18]   K. Kim, N. Selvapalam, Y. H. Ko, K. M. Park, D. Kim, J. Kim, Chem. Soc. Rev. 2007, 36,  267.
        | CrossRef |   

[19]   T. Matsue, D. H. Evans, T. Osa, N. Kobayashi, J. Am. Chem. Soc. 1985, 107,  3411.
        | CrossRef |   

[20]   Bard A. J., Faulkner L. R., Electrochemical Methods, Fundamentals and Applications, 2nd edn 2001, Ch. 2 (Wiley: New York, NY).

[21]   B. Siegel, R. Breslow, J. Am. Chem. Soc. 1975, 97,  6869.
        | CrossRef |   

[22]   A. Harada, S. Takahashi, J. Chem. Soc. Chem. Commun. 1984,  645.
        | CrossRef |   

[23]   R. Isnin, C. Salam, A. E. Kaifer, J. Org. Chem. 1991, 56,  35.
        | CrossRef |   

[24]   L. A. Godínez, S. Patel, C. M. Criss, A. E. Kaifer, J. Phys. Chem. 1995, 99,  17449.
        | CrossRef |   

[25]   E. Coutouli-Argyropoulou, A. Kelaidopoulou, C. Sideris, G. Kokkinidis, J. Electroanal. Chem. 1999, 477,  130.
        | CrossRef |   

[26]   D. Osella, A. Carretta, C. Nervi, M. Ravera, R. Gobetto, Organometallics 2000, 19,  2791.
        | CrossRef |   

[27]   C. M. Cardona, T. D. McCarley, A. E. Kaifer, J. Org. Chem. 2000, 65,  1857.
        | CrossRef |   

[28]   P. R. Ashton, V. Balzani, M. Clemente-Leon, B. Colonna, A. Credi, N. Jayaraman, F. M. Raymo, J. F. Stoddart, M. Venturi, Chem. Eur. J. 2002, 8,  673.
        | CrossRef |   

[29]   R. Castro, I. Cuadrado, B. Alonso, C. M. Casado, M. Morán, A. E. Kaifer, J. Am. Chem. Soc. 1997, 119,  5760.
        | CrossRef |   

[30]   M. J. W. Ludden, D. N. Reinhoudt, J. Huskens, Chem. Soc. Rev. 2006, 35,  1122.
        | CrossRef |   

[31]   Y. Wang, S. Mendoza, A. E. Kaifer, Inorg. Chem. 1998, 37,  317.
        | CrossRef |   

[32]   B. González, C. M. Casado, B. Alonso, I. Cuadrado, M. Morán, Y. Wang, A. E. Kaifer, Chem. Commun. 1998,  2569.
         

[33]   B. González, I. Cuadrado, B. Alonso, C. M. Casado, M. Morán, A. E. Kaifer, Organometallics 2002, 21,  2569.
         

[34]   A. Mirzoian, A. E. Kaifer, Chem. Eur. J. 1997, 3,  1052.
        | CrossRef |   

[35]   C. Lee, M. S. Moon, J. W. Park, J. Inclusion Phenom. Mol. Recognit. Chem. 1996, 26,  219.
        | CrossRef |   

[36]   J. Kim, I.-S. Jung, S. Y. Kim, E. Lee, J.-L. Kang, S. Sakamoto, K. Yamaguchi, K. Kim, J. Am. Chem. Soc. 2000, 122,  540.
        | CrossRef |   

[37]   H.-J. Kim, W. S. Jeon, Y. H. Ko, K. Kim, Proc. Natl. Acad. Sci. USA 2002, 99,  5007.
        | CrossRef |   

[38]   W. Ong, M. Gómez-Kaifer, A. E. Kaifer, Org. Lett. 2002, 4,  1791.
        | CrossRef |   

[39]   W. Ong, A. E. Kaifer, J. Org. Chem. 2004, 69,  1383.
        | CrossRef |   

[40]   Y. Ling, J. T. Mague, A. E. Kaifer, Chem. Eur. J. 2007, 13,  7908.
        | CrossRef |   

[41]   Y. J. Jeon, H.-J. Kim, C. Lee, K. Kim, Chem. Commun. 1828,  2002.
         

[42]   J. Moon, J. Grindstaff, D. Sobransingh, A. E. Kaifer, Angew. Chem. Int. Ed. 2004, 43,  5496.
        | CrossRef |   

[43]   W. Wang, A. E. Kaifer, Angew. Chem. Int. Ed. 2006, 45,  7042.
        | CrossRef |   

[44]   W. Ong, A. E. Kaifer, Organometallics 2003, 22,  4181.
        | CrossRef |   

[45]   L. Cui, S. Gadde, W. Li, A. E. Kaifer, Langmuir 2009, 25,  13763.
        | CrossRef |   

[46]   L. Yuan, D. H. Macartney, J. Phys. Chem. B 2007, 111,  6949.
        | CrossRef |   

[47]   L. M. Tunstad, J. A. Tucker, E. Dalcanale, J. Weiser, J. A. Bryant, J. C. Sherman, R. C. Helgeson, C. B. Knobler, D. J. Cram, J. Org. Chem. 1989, 54,  1305.
        | CrossRef |   

[48]   Cram D. J., Cram J. M., Stoddart J. F. (Eds), Container Molecules and Their Guests, in Monographs in Supramolecular Chemistry Vol. 4 1994 (Royal Society of Chemistry: Cambridge).

[49]   S. Mendoza, P. D. Davidov, A. E. Kaifer, Chem. Eur. J. 1998, 4,  864.
        | CrossRef |   

[50]   L. R. MacGillivray, J. L. Atwood, Nature 1997, 389,  469.
        | CrossRef |   

[51]   A. Shivanyuk, J. Rebek, Proc. Natl. Acad. Sci. USA 2001, 98,  7662.
        | CrossRef |   

[52]   I. Philip, A. E. Kaifer, J. Org. Chem. 2005, 70,  1558.
        | CrossRef |   

[53]   L. Avram, Y. Cohen, Org. Lett. 2003, 5,  2329.
         

[54]   L. Avram, Y. Cohen, J. Am. Chem. Soc. 2003, 125,  16180.
        | CrossRef |   

[55]   I. Philip, A. E. Kaifer, J. Am. Chem. Soc. 2002, 124,  12678.
        | CrossRef |   

[56]   H. Mansikkamaki, C. A. Schalley, M. Nissinen, K. Rissanen, New J. Chem. 2005, 29,  116.
        | CrossRef |   

[57]   E. Mileo, S. Yi, P. Bhattacharya, A. E. Kaifer, Angew. Chem. Int. Ed. 2009, 48,  5337.
        | CrossRef |   

[58]   C. L. D. Gibb, B. Gibb, J. Am. Chem. Soc. 2004, 126,  11408.
        | CrossRef |   

[59]   S. M. Biros, E. C. Ullrich, F. Hoff, L. Trembelau, J. Rebek, J. Am. Chem. Soc. 2004, 126,  2870.
        | CrossRef |   

[60]   D. Podkoscielny, I. Philip, C. D. L. Gibb, B. C. Gibb, A. E. Kaifer, Chem. Eur. J. 2008, 14,  4704.
        | CrossRef |   

[61]   D. Podkoscielny, R. J. Hooley, J. Rebek, A. E. Kaifer, Org. Lett. 2008, 10,  2865.
        | CrossRef |   



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