Journal of Chemical Sciences

, Volume 114, Issue 6, pp 565–578 | Cite as

A new family of donor-acceptor systems comprising tin(IV) porphyrin and anthracene subunits: Synthesis, spectroscopy and energy transfer studies



A new family of covalently linked ‘Sn(IV) porphyrin-anthracene’ diad (1), triad (2) and tetrad (3) donor-acceptor (D-A) systems have been designed and synthesized in good-to-moderate yields. While diad 1 possesses one anthracene subunit at the peripheral (meso) position of the tin(IV) porphyrin scaffold, triad 2 possesses twotrans axial anthracene subunits at the tin(IV) centre. On the other hand, tetrad 3 is endowed with both the peripheral and axial anthracene subunits in its architecture. These D-A systems have been fully characterised by elemental analysis, FAB-MS, UV-Vis,1H and13C NMR and electrochemical methods. UV-Vis,NMR and redox data suggest the absence of intramolecular π-π interaction between the porphyrin and the anthracene/s in 1–3. Fluorescence from the anthracene subunit in 1 and 3 is found to be quenched in comparison with the fluorescence of free anthracene in four different solvents. This is not the case with compound 2. Excitation spectral data provides evidence for an intramolecular excitation energy transfer (EET) from the singlet anthracene to the porphyrin in 1 and 3. The energy transfer efficiency is in the order: 2 (almost negligible) < 3 (~30%) < 1 (nearly quantitative), with the peripheral anthracene → porphyrin pathway being largely favoured. This orientation dependence of EET could be analysed using Forster's dipole dipole mechanism.


Tin (IV) porphyrin anthracene spectroscopy energy transfer orientation dependence 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Ambroise A, Li J, Yu L and Lindsey J S 2000Org. Lett. 2 2563CrossRefGoogle Scholar
  2. 2.
    Yeow E K L, Sintic P J, Cabral N M, Reek J N H, Crossley M J and Ghiggino KP 2000Phys.Chem. Chem. Phys. 2 4281CrossRefGoogle Scholar
  3. 3.
    Osuka A, Shin J-Y, Yoneshima R, Shiratori H, Ohno T, Nozaki K, Nishimura Y, Yamazaki I, Taniguchi S, Shimizu T and Okada T 1999J. Porphyrins Phthalocyanines 3 729CrossRefGoogle Scholar
  4. 4.
    Brodard P, Matzinger S, Vauthey E, Mongin O, Papamicaeel C and Gossauer A 1999J. Phys. Chem. A103 5858Google Scholar
  5. 5.
    Flamigni L, Barigelletti F, Armaroli N, Ventura B, Collin J-P, Sauvage J-P and Williams JAG 1999Inorg. Chem. 38 661CrossRefGoogle Scholar
  6. 6.
    Kils K, Kajanus J, Mrtensson J and Albinsson B 1999J. Phys. Chem. B103 7329Google Scholar
  7. 7.
    Hermant R, Liddell P A, Lin S, Alden R G, Kang H K, Moore A L, Moore T AandGust D 1993J. Am. Chem. Soc. 115 2080CrossRefGoogle Scholar
  8. 8.
    Osuka A, Yamada H, Maruyama K, Mataga N, Asahi O M T, Okada T, Yamazaki I and Nishimura Y 1993J. Am. Chem. Soc. 115 9439CrossRefGoogle Scholar
  9. 9.
    Lindsey J S, Brown P A and Siesel D A 1989Tetrahedron 45 4845CrossRefGoogle Scholar
  10. 10.
    Effenberger F, Schlosser H, Bauerle P, Maier S, Port H and Wolf H C 1988Angew. Chem., Int. Ed. Engl. 27 281CrossRefGoogle Scholar
  11. 11.
    Giribabu L, Kumar A A, Neeraja V and Maiya B G 2001Angew. Chem. (Int. Ed.) 40 3621CrossRefGoogle Scholar
  12. 12.
    Lindsey J S, Schreiman I C, Hsu H C, Kearney P C and Marguerettaz A M 1987J. Org. Chem. 52 827CrossRefGoogle Scholar
  13. 13.
    Kadish K M, Xu Q Y, Maiya B G, Barbe J-M and Guilard R 1989J. Chem. Soc., Dalton Trans. 1531Google Scholar
  14. 14.
    Moghadam G E, Ding L, Tadj F and Meunier B 1989Tetrahedron 45 2641CrossRefGoogle Scholar
  15. 15.
    Sirish M and Maiya B G 1995J. Photochem. Photobiol. A88 127CrossRefGoogle Scholar
  16. 16.
    Perrin D D, Armarego W L F and Perrin D R 1986Purification of laboratory chemicals (Oxford: Pergamon)Google Scholar
  17. 17.
    Harriman A and Davila J 1989Tetrahedron 45 4737CrossRefGoogle Scholar
  18. 18.
    Murov S L 1973Handbook of photochemistry (New York: Marcel Dekker)Google Scholar
  19. 19.
    Lackowicz J R 1983Principles of fluorescence spectroscopy (New York: Plenum)Google Scholar
  20. 20.
    Rao T A and Maiya B G 1996Inorg. Chem. 35 4829CrossRefGoogle Scholar
  21. 21.
    Giribabu L, Rao T A and Maiya B G 1999Inorg. Chem. 38 4971CrossRefGoogle Scholar
  22. 22.
    Sirish M, Kache R and Maiya B G 1996J. Photochem. Photobiol. A93 129Google Scholar
  23. 23.
    Giribabu L and Maiya B G 1999Res. Chem. Intermed. 25 769CrossRefGoogle Scholar
  24. 24.
    Sirish M and Maiya BG 1998J. Porphyrins. Phthalocyanins 2 327CrossRefGoogle Scholar
  25. 25.
    Reddy D R and Maiya B G 2001Chem. Commun. 117 Google Scholar
  26. 26.
    Guilard R, Ratti C, Barbe J M and Kadish K M 1991Inorg. Chem. 30 1537CrossRefGoogle Scholar
  27. 27.
    Hawley J C 1998 Ph D thesis, University of Cambridge, Cambridge, UKGoogle Scholar
  28. 28.
    Buchler J W, Puppe L, Rohbock K and Schneehage H H 1973Chem. Ber. 106 2710CrossRefGoogle Scholar
  29. 29.
    Singh A K and Roy M 1991J. Photochem. Photobiol. B8 325Google Scholar
  30. 30.
    Arnold D P and Bartley J P 1994Inorg. Chem. 33 1486CrossRefGoogle Scholar
  31. 31.
    Abraham R J, Bedford G R, McNeillie D and Wright B 1980Org. Magn. Reson. 14 418CrossRefGoogle Scholar
  32. 32.
    Hawley J C, Bampos N, Abraham R J and Sanders J K M 1998Chem. Commun. 661Google Scholar
  33. 33.
    Nicholson R S and Shain I 1964Anal. Chem. 36 706CrossRefGoogle Scholar
  34. 34.
    Kadish K M 1986Prog. Inorg. Chem. 34 435CrossRefGoogle Scholar
  35. 35.
    Hirakawa K and Segawa H 1999J. Photochem. Photobiol. A123 67CrossRefGoogle Scholar
  36. 36.
    Forster Th 1959Discuss. Faraday Soc. 27 7CrossRefGoogle Scholar
  37. 37.
    Dexter D L 1953J. Chem. Phys. 21 836CrossRefGoogle Scholar
  38. 38.
    Scholes GD, Ghiggino KP, Oliver A M and Paddon-Row M N 1973J. Phys. Chem. 97 11871CrossRefGoogle Scholar
  39. 39.
    Gouterman M 1961J. Mol. Spectrosc. 6 138CrossRefGoogle Scholar
  40. 40.
    deSilva A P and Rice T E J 1999Chem. Commun. 163Google Scholar
  41. 41.
    Fox M A and Galoppini E 1997J. Am. Chem. Soc. 119 5277CrossRefGoogle Scholar
  42. 42.
    Sucheta A, Ackreli BAC, Cochran B and Armstrong F 1992Nature (London) 356 361CrossRefGoogle Scholar
  43. 43.
    Martin A S and Sambles J R 1996Nanotechnology 7 401CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2002

Authors and Affiliations

  • A. Ashok kumar
    • 1
  • L. Giribabu
    • 1
  • Bhaskar G. Maiya
    • 1
  1. 1.School of ChemistryUniversity of HyderabadHyderabadIndia

Personalised recommendations