Skip to main content
Log in

Charge Transfer Photophysics of Tetra(α-amino) Zinc Phthalocyanine

  • Original Paper
  • Published:
Journal of Fluorescence Aims and scope Submit manuscript

Abstract

The absorption, fluorescence, and transient absorption spectra of Tetra(α-amino) zinc phthalocyanine, ZnPc(α-NH2)4, have been measured in polar solvents and compared with that of ZnPc(α-R)4 (R = H, NO2, OCH(CH3)2). While the latter three showed the typical photophysics of phthalocyanines, ZnPc(α-NH2)4 exhibits distinct spectral properties, a very low fluorescence quantum yield and a relatively long fluorescence lifetime. These observations are explained by the substantial charge transfer characters in the absorption and fluorescence spectra of ZnPc(α-NH2)4. NMR indicates that intramolecular H-bonding makes atoms in NH2 actually coplanar with other elements of ZnPc(α-NH2)4. The local excited state is non emissive and the weak emission is assigned to its charge transfer state. The transient absorption bands from laser flash photolysis located at 630 nm, 645 nm is assigned to the mono-charge transfer state, while that at 545 nm is assigned to the di-charge transfer state.

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

Access this article

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

Instant access to the full article PDF.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Gómez-Hens A, Aguilar-Caballos MP (2004) Long-wavelength fluorophores new trends in their analytical use. Trends Analyt Chem 23:127–136. doi:10.1016/S0165-9936(04)00305-X

    Article  Google Scholar 

  2. Chen XL, Li ZB, Zhu YX, Xu JG (2004) Sensitive fluorimetric method for the determination of aniline by using tetra-substituted amino aluminium phthalocyanine. Anal Chim Acta 505:283–287. doi:10.1016/j.aca.2003.10.067

    Article  CAS  Google Scholar 

  3. Chen XL, Yang HH, Zhu QZ, Zheng H, Xu JG, Li DH (2001) A new red-region substrate, tetra-substituted amino aluminium phthalocyanine, for the fluorimetric determination of H2O2 catalyzed by mimetic peroxidases. Analyst (Lond.) 126:523–527. doi:10.1039/b009253n

    Article  CAS  Google Scholar 

  4. Zhan XQ, Li DH, Zhu QZ, Xu JG, Zheng H (2000) Sensitive fluorimetric determination of formaldehyde by the co-quenching effect of formaldehyde and sulfite on the fluorescence of tetra-substituted amino aluminium phthalocyanine. Analyst (Lond.) 125:2330–2334. doi:10.1039/b005432l

    Article  CAS  Google Scholar 

  5. Chen XL, Li DH, Yang HH, Zhu QZ, Zheng H, Xu JG (2001) Study of tetra-substituted amino aluminum phthalocyanine as a new red-region substrate for the fluorometric determination of peroxidase and hydrogen peroxide. Anal Chim Acta 434:51–58. doi:10.1016/S0003-2670(01)00819-4

    Article  CAS  Google Scholar 

  6. Mortimer RJ, Dyer AL, Reynolds JR (2006) Electrochromic organic and polymeric materials for display applications. Displays 27:2–18. doi:10.1016/j.displa.2005.03.003

    Article  CAS  Google Scholar 

  7. Jung SH, Choi JH, Yang SM, Cho WJ, Ha CS (2001) Syntheses and characterization of soluble phthalocyanine derivatives for organic electroluminescent devices. Mater Sci Eng B 85:160–164. doi:10.1016/S0921-5107(01)00600-6

    Article  Google Scholar 

  8. Mortimer RJ (1999) Organic electrochromic materials. Electrochim Acta 44:2971–2981. doi:10.1016/S0013-4686(99)00046-8

    Article  CAS  Google Scholar 

  9. Lunardi CN, Tedesco AC (2005) Synergic photosensitizers: a new trend in photodynamic therapy. Curr Org Chem 9:813–821. doi:10.2174/1385272053764944

    Article  CAS  Google Scholar 

  10. WenXing C, ShiLiang C, ShenShui L, YuYuan YAO, MinHong XU (2007) Photocatalytic oxidation of phenol in aqueous solutions with oxygen catalyzed by supported metallophthalo-cyanine catalyst. Sci China, Ser Biol Chem 50:379–384

    Article  Google Scholar 

  11. Ishil K, Kobayashi N (2003) The photophysical properties of phthalocyanines and related compounds. In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook. Academic Press, San Diego, pp 1–42

    Google Scholar 

  12. Nyokong T (2007) Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines. Coord Chem Rev 251:1707–1722. doi:10.1016/j.ccr.2006.11.011

    Article  CAS  Google Scholar 

  13. Tedesco AC, Rotta JCG, Lunardi CN (2003) Synthesis, photophysical and photochemical aspects of phthalocyanines for photodynamic therapy. Curr Org Chem 7:187–196. doi:10.2174/1385272033373076

    Article  CAS  Google Scholar 

  14. Ferraudi G (1989) Photochemical properties of metallophthalocyanines in homogeneous solution. In: Leznoff CC, Lever ABP (eds) Phthalocyanines: properties and applications. VCH, New York

    Google Scholar 

  15. Zhang X-F, Xu H (1993) Influence of halogenation and aggregation on photosensitizing properties of zinc phthalocyanine (ZnPC). J Chem Soc, Faraday Trans 89:3347–3351. doi:10.1039/ft9938903347

    Article  CAS  Google Scholar 

  16. Zhang X-F, Xu H (1994) Synthesis and photophysical properties of substituted zinc phthalocyanines. Chem Res Chin Univ 15:917–921

    CAS  Google Scholar 

  17. Zhang X-F, Ma J, Xu H (1993) Photophysical properties of some water soluble metal phthalocyanines. Proc. SPIE 1616:372–375. doi:10.1117/12.137035

    Article  CAS  Google Scholar 

  18. Zhang X-F, Cui X, Liu Q, Zhang F (2008) Multiple-charge separation in nanoscale artificial photosynthetic models. ChemPhysChem 9:1514–1518. doi:10.1002/cphc.200800191

    Article  CAS  PubMed  Google Scholar 

  19. Seybold PG, Gouterman M (1969) Porphyrins XIII: fluorescence spectra and quantum yields. J Mol Spectrosc 31:1–13. doi:10.1016/0022-2852(69)90335-X

    Article  CAS  Google Scholar 

  20. Ouedraogo GV, More C, Richard Y, Benlian D (1981) Charge-transfer and Moessbauer spectra of axially substituted iron phthalocyanines. Inorg Chem 20:4387–4393. doi:10.1021/ic50226a069

    Article  CAS  Google Scholar 

  21. Dale BW (1969) Effect of axial ligands upon the electronic absorption spectrum of phthalocyanineiron(II). Trans Faraday Soc 65:331–339. doi:10.1039/tf9696500331

    Article  CAS  Google Scholar 

  22. Chen H, Jiang Y-B (2000) Photophysics of 1-dimethylaminonaphthalene in aqueous-organic binary solvents. Chem Phys Lett 325:605–609. doi:10.1016/S0009-2614(00)00741-7

    Article  CAS  Google Scholar 

  23. Barik A, Kumbhakar M, Nath S, Pal H (2005) Evidence for the TICT mediated nonradiative deexcitation process for the excited coumarin-1 dye in high polarity protic solvents. Chem Phys 315:277–285. doi:10.1016/j.chemphys.2005.04.018

    Article  CAS  Google Scholar 

  24. Inokuma Y, Easwaramoorthi S, Yoon ZS, Kim D, Osuka A (2008) meso-(4-(N, N-Dialkylamino)phenyl)-substituted subporphyrins: remarkably perturbed absorption spectra and enhanced fluorescence by intramolecular charge transfer interactions. J Am Chem Soc 130:12234–12235. doi:10.1021/ja804846v

    Article  CAS  PubMed  Google Scholar 

  25. Druzhinin SI, Bursulaya BD, Uzhinov BM (1995) Planar and twisted intramolecular charge transfer states of the excited proton transfer products of aminocoumarins. J Photochem Photobiol A 90:53–56

    Article  CAS  Google Scholar 

  26. Maslov VG, Sidorov AN (1974) The photochemical generation of negative phthalocyanine and porphyrin ions. Theor Exp Chem 7:680–683. doi:10.1007/BF00524988

    Article  Google Scholar 

  27. Ishil K, Kobayashi N (2003) The photophysical properties of phthalocyanines and related compounds. In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook. Academic Press, San Diego, pp 1–42

    Google Scholar 

  28. Bishop SM, Beeby A, Parker AW, Foley DPMSC (1995) The preparation and photophysical measurements of perdeutero zinc phthalocyanine. J Photochem Photobiol A 90:39–44

    Article  CAS  Google Scholar 

  29. Mack J, Stillman MJ (2001) Assignment of the optical spectrum of metal porphyrin and phthalocyanine radical anions. J Porphyrins Phthalocyanines 5:67–71. doi:10.1002/1099-1409(200101)5:1<67::AID-JPP300>3.0.CO;2-3

    Article  CAS  Google Scholar 

  30. Mack J, Kobayashi N, Stillman MJ (2006) Magnetic circular dichroism spectroscopy and TD-DFT calculations of metal phthalocyanine anion and cation radical species. J Porphyrins Phthalocyanines 10:1219

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank HBUST and the Key Laboratory of Photochemistry, Chinese Academy of Sciences for financial support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Xian-Fu Zhang.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, XF., Li, X., Niu, L. et al. Charge Transfer Photophysics of Tetra(α-amino) Zinc Phthalocyanine. J Fluoresc 19, 947–954 (2009). https://doi.org/10.1007/s10895-009-0494-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10895-009-0494-7

Keywords

Navigation