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Spectroscopic Study of the Dimerization Process οf Iron Protoporphyrin IX

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Dziedzic-Kocurek K., Byrne H., Świderski A., Stanek J.

Acta Physica Polonica A

2009

vol. 115

issue 2

552-555

The commercial protoporphyrin IX, iron-ferriprotoporphyrin IX-chloride and synthesized iron porphyrin μ-oxo-dimers were examined by UV/vis absorption and fluorescence, Fourier transformed infrared spectroscopy, resonance Raman, X-ray absorption, Mössbauer spectroscopy and SQUID. The evidence of Fe-O-Fe antiferromagnetic coupling concluded from SQUID and Mössbauer in the case of samples containing dimerized forms confirmed the presence of the oxo-bridges. In this paper the results of UV/vis, fluorescence, Fourier transform infrared FTIR and Raman spectroscopies are reported and discussed. The study is based on the comparison of the free-base protoporphyrin IX, Fe-PPIX-Cl and the synthesized dimerized specimen. The vibrational modes in two energy regions i.e. 330-650 cm^{-1} and 750-900 cm^{-1}, reportedly characteristic of the existence of Fe-O-Fe bridges, are discussed. A significant photoluminescence emission, strongly Stokes shifted from the Soret band, absent in the protoporphyrin IX and the iron-ferriprotoporphyrin IX-chloride, is observed. The strong Stokes shift and the mismatch of the excitation spectrum to the Soret band suggest that is does not have origin in the de-excitation of the porphyrin moiety and that it could have origin in an Fe-O-Fe charge transfer state.

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1 Acta Physica Polonica A

1 2009

1 Byrne H.

1 Dziedzic-Kocurek K.

1 Stanek J.

1 Świderski A.

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Spectroscopic Study of the Dimerization Process οf Iron Protoporphyrin IX