Journal of Solution Chemistry

, Volume 39, Issue 9, pp 1327–1340 | Cite as

Photophysical Investigations on Determination of Ionicity and Electronic Structures for the Non-covalent Complexes of Calix[4]resorcinarene with Fullerenes C60 and C70 in the Solution State

  • Amal Halder
  • Dulal C. Mukherjee
  • Sumanta Bhattacharya
Article
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Abstract

Ground state non-covalent interactions between a macrocyclic receptor, C-methylcalix[4]resorcinarene (1) and fullerenes (C60 and C70) have been studied in benzonitrile by an absorption spectrophotometric method. Absorption bands are located in the visible region due to the charge transfer (CT) transition between 1 and various electron acceptors (including fullerenes), namely, 2,3-dichloro-5,6-dicyano-p-benzoquinone, tetracyanoquinodimethane and p-chloranil. Utilizing the CT absorption bands, various important physicochemical parameters, including oscillator strength, resonance energy, transition dipole strength of all the acceptor-1 complexes and vertical ionization potential of 1 are determined. Job’s method of continuous variation reveals 1:1 stoichiometry between fullerenes and 1. The most fascinating feature of the present study is that 1 binds selectively to C70 compared to C60 as obtained from binding constant (K) data of C60-1 (\(K_{\mathrm{C}60\mbox{-}\mathbf{1}}\)) and C70-1 (\(K_{\mathrm{C}70\mbox{-}\mathbf{1}}\)) complexes, i.e., \(K_{\mathrm{C}60\mbox{-}\mathbf{1}}=190\) dm3⋅mol−1 and \(K_{\mathrm{C}70\mbox{-}\mathbf{1}}=5{,}800\) dm3⋅mol−1 and selectivity (KC70-1 /KC60-1 ) ∼30. Quantum chemical calculations based on hybrid density functional theory estimate the enthalpies of formation of the fullerene-1 complexes in vacuo and provide very good support for selectivity in the K values of the C70 and C60 complexes of 1. The exchange and correlation energies have been calculated using a hybrid DFT functional method. We have opted to use the hybrid DFT functional over the Hartree-Fock method, as it can account for correlation effects also. Molecular electrostatic potential map calculations give a clear picture on the electronic structures of the fullerene-1 complexes.

Keywords

Fullerenes C60 and C70 C-methylcalix[4]resorcinarene UV-Vis spectroscopic technique Charge transfer absorption band Binding constant Hybrid DFT calculations 
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References

  1. 1.
    Corbellini, F., Fiammengo, R., Timmerman, P., Calama, M.C., Versluis, K., Heck, A.J.R., Luyten, I., Reinhoudt, D.N.: Guest encapsulation and self-assembly of molecular capsules in polar solvents via multiple ionic interactions. J. Am. Chem. Soc. 124, 6569–6575 (2002) CrossRefGoogle Scholar
  2. 2.
    Atwood, J.L., Barbour, L.J., Jerga, A.: Organization of the interior of molecular capsules by hydrogen bonding. Proc. Natl. Acad. Sci. USA 99, 4837–4841 (2002) CrossRefGoogle Scholar
  3. 3.
    Tunstad, L.M., Tucker, J.A., Dalcanale, E., Weiser, J., Bryant, J.A., Sherman, J.C., Helgeson, R.C., Knobler, C.B., Cram, D.J.: Host-guest complexation. 48. Octol building blocks for cavitands and carcerands. J. Org. Chem. 54, 1305–1312 (1989) CrossRefGoogle Scholar
  4. 4.
    Ma, B.Q., Zhang, Y., Coppens, P.: Multiple structures in supramolecular solids: benzophenone embedded in three different C-methylcalix[4]resorcinarene/bipyridine frameworks. Cryst. Growth Des. 1, 271–275 (2001) CrossRefGoogle Scholar
  5. 5.
    MacGillivray, L.R., Spinney, H.A., Reid, J.L., Ripmeester, J.A.: Entrapment of ferrocenes within supramolecular, deep-cavity resorcin[4]arenes. Chem. Commun., 517–518 (2000) Google Scholar
  6. 6.
    Solari, E., Lesueur, W., Klose, A., Schenk, K., Floriani, C., Villa, A.C., Rizzoli, C.: A square array of metal ions from the full metallation of calix[4]resorcinarenes. Chem. Commun., 807–808 (1996) Google Scholar
  7. 7.
    Atwood, J.L., Barbour, L.J., Hardie, M.J., Lygris, E., Raston, C.L., Webb, H.R.: Inclusion complex of 18-crown-6 and (Na+⊂[2.2.2]cryptand) in [C-methylcalix[4]resorcinarene-Hn]. Cryst. Eng. Commun. 3, 41–43 (2001) Google Scholar
  8. 8.
    Kuznetsova, L.S., Mustafina, A.R., Ziganshina, A.Y., Kazakova, E.K., Konovalov, A.I.: The synergistic extraction of lanthanide ions by a mixture of calix[4]resorcinarene or its dimethylamino-, piperidyl- or trimethylammoniummethylated derivative and 1,10-phenanthroline in n-heptanol. J. Incl. Phenom. Macrocycl. Chem. 39, 65–69 (2001) CrossRefGoogle Scholar
  9. 9.
    Atwood, J.L., Barbour, L.J., Ness, T.J., Raston, C.L., Raston, P.L.: A well-resolved ice-like (H2O)8 cluster in an organic supramolecular complex. J. Am. Chem. Soc. 123, 7192–7193 (2001) CrossRefGoogle Scholar
  10. 10.
    MacGillivray, L.R., Papaefstathiou, G.S., Reid, J.L., Ripmeester, J.A.: A rod-shaped guest leads to architectural isomerism in a multicomponent crystalline framework based on a resorcin[4]arene. Cryst. Growth Des. 1, 373–375 (2001) CrossRefGoogle Scholar
  11. 11.
    Ma, B.Q., Zhang, Y., Coppens, P.: structural variation and supramolecular isomerism in the C- methylcalix[4]resorcinarene/bipyridine system. Cryst. Growth Des. 2, 7–13 (2002) CrossRefGoogle Scholar
  12. 12.
    Cave, G.W.V., Hardie, M.J., Roberts, B.A., Raston, C.L.: Versatile six-component molecular capsule based on benign synthons—selective confinement of a heterogeneous molecular aggregate. Eur. J. Org. Chem. 2001, 3227–3231 (2001) CrossRefGoogle Scholar
  13. 13.
    Fleischer, M., Panteleit, F., Wharam, D.A.: Fabrication of nanostructures using a C-methylcalix[4]resorcinarene dielectric spacer. J. Vac. Sci. Technol. B 25, 877–880 (2007) CrossRefGoogle Scholar
  14. 14.
    Fleischer, M., Panteleit, F., Schefzyk, D.J., Ritchie, D.A., Pepper, M., Wharam, D.A.: A tunable three-lead double quantum dot with a resorcinarene spacer. Semicond. Sci. Technol. 24, 025010 (2009) CrossRefGoogle Scholar
  15. 15.
    Gutsche, C.D.: In: Stoddart, J.F.E. (ed.) Calixarenes Revisited. Monographs in Supramolecular Chemistry. The Royal Society of Chemistry, Cambridge (1998) Google Scholar
  16. 16.
    Bhattacharya, S., Nayak, S.K., Chattopadhyay, S., Banerjee, M., Mukherjee, A.K.: Spectrophotometric and thermodynamic study of supramolecular complexes of [60]- and [70]fullerenes with a number of calix[n]arenas. J. Chem. Soc. Perkin Trans. 2, 2292–2297 (2001) Google Scholar
  17. 17.
    Bhattacharya, S., Semwal, A., Nayak, S.K., Chattopadhyay, S., Banerjee, M.: Study of host–guest interaction of [70]fullerene with substituted calix[6]arenes by absorption spectrometric method. J. Phys. Chem. A 108, 9064–9068 (2004) CrossRefGoogle Scholar
  18. 18.
    Bhattacharya, S., Sharma, A., Nayak, S.K., Chattopadhyay, S., Mukherjee, A.K.: NMR study of complexation of crown ethers with [60] and [70]fullerenes. J. Phys. Chem. A 107, 4213–4217 (2003) Google Scholar
  19. 19.
    Bhattacharya, S., Sharma, A., Nayak, S.K., Chattopadhyay, S., Mukherjee, A.K.: Vertical ionisation potentials of a number of crown ethers from charge transfer bands of their EDA complexes. Spectrochim. Acta A 58, 2841–2848 (2002) CrossRefGoogle Scholar
  20. 20.
    Bhattacharya, S., Nayak, S.K., Chattopadhyay, S., Saha, D.: Supramolecular fullerene/porphyrin interactions: a rational approach towards charge transfer absorption and emission analyzed by electronic coupling theory. J. Mol. Liq. 143, 125–128 (2008) CrossRefGoogle Scholar
  21. 21.
    Mukherjee, S., Bauri, A.K., Bhattacharya, S.: Investigations on photophysical properties and binding strength for the supramolecular complexes of newly designed diporphyrins with fullerenes. J. Mol. Struct. 965, 101–108 (2010) CrossRefGoogle Scholar
  22. 22.
    Ray, A., Goswami, D., Chattopadhyay, S., Bhattacharya, S.: Photophysical and theoretical investigations on fullerene/phthalocyanine supramolecular complexes. J. Phys. Chem. A 112, 11627–11640 (2008) CrossRefGoogle Scholar
  23. 23.
    Ray, A., Santhosh, K., Chattopadhyay, S., Samanta, A., Bhattacharya, S.: Spectroscopic and theoretical investigations on effective and selective interaction of fullerenes C60 and C70 with a derivatized Zn phthalocyanine: stabilization of charge-recombined state by side-on approach of C70. J. Phys. Chem. A 114, 5544–5550 (2010) CrossRefGoogle Scholar
  24. 24.
    Ajie, H., Alvarez, M.M., Anz, S.Z., Beck, R.D., Diederich, F., Fostiropoulos, K., Huffman, D.K., Kratschmer, W., Rubin, Y., Shriver, K.E., Sensharma, D., Whetten, R.L.: Characterization of the soluble all-carbon molecules C60 and C70. J. Phys. Chem. 94, 8630–8633 (1990) CrossRefGoogle Scholar
  25. 25.
    Gasyna, Z., Schatz, P.N., Hare, J.P., Dennis, T.J., Kroto, H.W., Taylor, R., Walton, D.R.M.: The magnetic circular dichroism and absorption spectra of C60 isolated in Ar matrices. Chem. Phys. Lett. 183, 283–291 (1991) CrossRefGoogle Scholar
  26. 26.
    Leach, S., Vervloet, M., Despres, A., Breheret, E., Hare, J.P., Dennis, T.J., Kroto, H.W., Taylor, R., Walton, D.R.M.: Electronic spectra and transitions of the fullerene C60. Chem. Phys. 160, 451–466 (1992) CrossRefGoogle Scholar
  27. 27.
    Gould, I.R., Noukakis, D., Gomez-Jahn, L., Young, R.H., Goodman, J.L., Farid, S.: Radiative and nonradiative electron transfer in contact radical-ion pairs. Chem. Phys. 176, 439–456 (1993) CrossRefGoogle Scholar
  28. 28.
    Mulliken, R.S.: Molecular compounds and their spectra. II. J. Am. Chem. Soc. 74, 811–824 (1952) CrossRefGoogle Scholar
  29. 29.
    Bhattacharya, S., Banerjee, M., Mukherjee, A.K.: Study of the formation equilibria of electron donor–acceptor complexes between [60]fullerene and methylbenzenes by absorption spectrometric method. Spectrochim. Acta A 57, 1463–1470 (2001) CrossRefGoogle Scholar
  30. 30.
    Bhattacharya, S., Nayak, S.K., Chattopadhyay, S., Banerjee, M., Mukherjee, A.K.: Study of ground state EDA complex formation between [70]fullerene and a series of polynuclear aromatic hydrocarbons. Spectrochim. Acta A 58, 289–298 (2002) CrossRefGoogle Scholar
  31. 31.
    Peover, M.E.: A polarographic investigation into the redox behaviour of quinones: the roles of electron affinity and solvent. J. Chem. Soc. 4540–4549 (1962) Google Scholar
  32. 32.
    Bhattacharya, S., Banerjee, M., Mukherjee, A.K.: Room temperature solution studies of complexation between o-chloranil and a series of anilines by spectrophotometric method. Spectrochim. Acta A 57, 2409–2416 (2001) CrossRefGoogle Scholar
  33. 33.
    Foster, R.: Organic Charge Transfer Complexes, Chaps. 3, 13. Academic Press, New York (1969). Google Scholar
  34. 34.
    Briegleb, G.: Elektronenaffinitäten organischer Moleküle. Angew. Chem. 76, 326–341 (1964) CrossRefGoogle Scholar
  35. 35.
    Briegleb, G.: Elektronen-Donator-Acceptor-Komplexes. Springer, Berlin (1961) Google Scholar
  36. 36.
    Hare, J.P., Kroto, H.W., Taylor, R.: Preparation and UV/visible spectra of fullerenes C60 and C70. Chem. Phys. Lett. 177, 394–398 (1991) CrossRefGoogle Scholar
  37. 37.
    Taylor, R., Hare, J.P., Sada, A.K.A., Kroto, H.W.: Isolation, separation and characterisation of the fullerenes C60 and C70: the third form of carbon. J. Chem. Soc., Chem. Commun. 1423–1425 (1990) Google Scholar
  38. 38.
    Benesi, H.A., Hildebrand, J.H.: A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J. Am. Chem. Soc. 71, 2703–2707 (1949) CrossRefGoogle Scholar
  39. 39.
    Sibley, S.P., Campbell, R.L., Silber, H.B.: Solution and solid state interactions of C60 with substituted anilines. J. Phys. Chem. 99, 5274–5276 (1995) CrossRefGoogle Scholar
  40. 40.
    Mizyed, S., Ashram, M., Miller, D.O., Georghiou, P.E.: Supramolecular complexation of [60]fullerene with hexahomotrioxacalix[3]naphthalenes: a new class of naphthalene-based calixarenes. J. Chem. Soc. Perkin Trans. 2, 1916–1919 (2001) Google Scholar
  41. 41.
    Ikeda, A., Suzuki, Y., Yoshimura, M., Shinkai, S.: On the prerequisites for the formation of solution complexes from [60]fullerene and calix[n]arenes: a novel allosteric effect between [60]fullerene and metal cations in calix[n]aryl ester complexes. Tetrahedron 54, 2497–2508 (1998) CrossRefGoogle Scholar
  42. 42.
    Tsubaki, K., Tanaka, K., Kinoshita, T., Fuji, K.: Complexation of C60 with hexahomooxacalix[3]arenes and supramolecular structures of complexes in the solid state. Chem. Commun., 895–896 (1998) Google Scholar
  43. 43.
    Mizyed, S., Georghiou, P.E., Ashram, M.: Thermodynamic study of the complexes of calix[4]naphthalenes with [60]fullerene in different solvents. J. Chem. Soc. Perkin Trans. 2, 277–280 (2000) Google Scholar
  44. 44.
    Wang, M.X., Zhang, X.H., Zheng, Q.Y.: Synthesis, structure, and [60]fullerene complexation properties of azacalix[m]arene[n]pyridines. Angew. Chem., Int. Ed. 43, 838–842 (2004) CrossRefGoogle Scholar
  45. 45.
    Matsubara, H., Oguri, S., Asano, K., Yamamoto, K.: Syntheses of novel cyclotriveratrylenophane capsules and their supramolecular complexes of fullerenes. Chem. Lett. 28, 431–432 (1999) CrossRefGoogle Scholar
  46. 46.
    Dudic, M., Lhotak, P., Stibor, I., Petrıckova, H., Lang, K.: (Thia)calix[4]arene–porphyrin conjugates: novel receptors for fullerene complexation with C70 over C60 selectivity. New J. Chem. 28, 85–90 (2004) CrossRefGoogle Scholar
  47. 47.
    Haino, T., Yanase, M., Fukazawa, Y.: Fullerenes enclosed in bridged calix[5]arenas. Angew. Chem. Int. Ed. 37, 997–998 (1998) CrossRefGoogle Scholar
  48. 48.
    Shoji, Y., Tashiro, K., Aida, T.: Selective extraction of higher fullerenes using cyclic dimers of ZINC PORPhyrins. J. Am. Chem. Soc. 126, 6570–6571 (2004) CrossRefGoogle Scholar
  49. 49.
    Zheng, J.Y., Tashiro, K., Hirabayashi, Y., Kinbara, K., Saigo, K., Aida, T., Sakamoto, S., Yamaguchi, K.: Cyclic dimers of metalloporphyrins as tunable hosts for fullerenes: a remarkable effect of rhodium(III). Angew. Chem. Int. Ed. 40, 1857–1861 (2001) CrossRefGoogle Scholar
  50. 50.
    Komatsu, N.: Preferential precipitation of C70 over C60 with p-halohomooxacalix[3]arenas. Org. Biomol. Chem. 1, 204–209 (2003) CrossRefGoogle Scholar
  51. 51.
    Taylor, R.: Lecture Notes on Fullerene Chemistry. Imperial Press, London (1997) Google Scholar
  52. 52.
    Seminario, J.M., Zacarias, A.G., Tour, J.M.: Theoretical study of a molecular resonant tunneling diode. J. Am. Chem. Soc. 122, 3015–3020 (2000) CrossRefGoogle Scholar
  53. 53.
    Mazumdar, C., Mizuseki, H., Kawazoe, Y.: Molecular scale rectifier: theoretical study. J. Phys. Chem. A 105, 9454–9459 (2001) CrossRefGoogle Scholar
  54. 54.
    Becke, A.D.: Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993) CrossRefGoogle Scholar
  55. 55.
    Lee, C., Yang, W., Parr, R.G.: Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988) CrossRefGoogle Scholar
  56. 56.
    Bhattacharya, S., Hashimoto, M., Fujimoto, A., Kimura, T., Uno, H., Komatsu, N.: Photophysical properties of a novel Ni(II)-diporphyrin in presence of fullerenes: insights from experimental and theoretical studies. Spectrochim. Acta A 70, 416–424 (2008) CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Amal Halder
    • 1
  • Dulal C. Mukherjee
    • 2
  • Sumanta Bhattacharya
    • 1
  1. 1.Department of ChemistryThe University of Burdwan, GolapbagBurdwanIndia
  2. 2.Department of ChemistryHeritage Institute of Technology, AnandapurKolkataIndia

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