Skip to main content
SpringerLink
Log in

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

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

    We’re sorry, something doesn't seem to be working properly.

    Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

  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)

  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. 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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  Google Scholar 

  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. 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. 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)

    Article  CAS  Google Scholar 

  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)

    CAS  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  28. Mulliken, R.S.: Molecular compounds and their spectra. II. J. Am. Chem. Soc. 74, 811–824 (1952)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  Google Scholar 

  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)

  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)

    Article  CAS  Google Scholar 

  33. Foster, R.: Organic Charge Transfer Complexes, Chaps. 3, 13. Academic Press, New York (1969).

    Google Scholar 

  34. Briegleb, G.: Elektronenaffinitäten organischer Moleküle. Angew. Chem. 76, 326–341 (1964)

    Article  CAS  Google Scholar 

  35. Briegleb, G.: Elektronen-Donator-Acceptor-Komplexes. Springer, Berlin (1961)

    Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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. 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)

    Article  CAS  Google Scholar 

  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)

  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. 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)

    Article  CAS  Google Scholar 

  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)

    Article  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  47. Haino, T., Yanase, M., Fukazawa, Y.: Fullerenes enclosed in bridged calix[5]arenas. Angew. Chem. Int. Ed. 37, 997–998 (1998)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  50. Komatsu, N.: Preferential precipitation of C70 over C60 with p-halohomooxacalix[3]arenas. Org. Biomol. Chem. 1, 204–209 (2003)

    Article  CAS  Google Scholar 

  51. Taylor, R.: Lecture Notes on Fullerene Chemistry. Imperial Press, London (1997)

    Google Scholar 

  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)

    Article  CAS  Google Scholar 

  53. Mazumdar, C., Mizuseki, H., Kawazoe, Y.: Molecular scale rectifier: theoretical study. J. Phys. Chem. A 105, 9454–9459 (2001)

    Article  Google Scholar 

  54. Becke, A.D.: Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993)

    Article  CAS  Google Scholar 

  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)

    Article  CAS  Google Scholar 

  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)

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, The University of Burdwan, Golapbag, Burdwan, 713 104, India

    Amal Halder & Sumanta Bhattacharya

  2. Department of Chemistry, Heritage Institute of Technology, Anandapur, Kolkata, 700 017, West Bengal, India

    Dulal C. Mukherjee

Authors
  1. Amal Halder
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dulal C. Mukherjee
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Sumanta Bhattacharya
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sumanta Bhattacharya.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

(PDF 1.05 MB)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Halder, A., Mukherjee, D.C. & Bhattacharya, S. 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. J Solution Chem 39, 1327–1340 (2010). https://doi.org/10.1007/s10953-010-9590-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-010-9590-1

Keywords

Search

Navigation