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Clay-porphyrin systems: spectroscopic evidence of TMPyP Protonation, non-planar distortion and meso substituent rotation

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The interaction of the water-soluble 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine (TMPyP) with different 2:1 phyllosilicates was examined by Raman and UV-visible spectroscopies. The clay samples were saturated with the tetracationic porphyrin and isolated from the aqueous suspension. A red shift of the Soret band was observed for all the clay-TMPyP systems in the order vermiculite < Laponite < mica-smectite (Syn-1) < montmorillonite (SWy-2). Furthermore, three components were observed for the Soret band (at ∼425, 455 and 488 nm). Raman spectra of the isolated solids excited at 457.9 nm, 488.0 nm and 514.5 nm suggest the occurrence of porphyrin protonation, non-planar distortion and rotation of the meso substituent. Based on the vibrational data, an acidity scale was proposed for the clays: vermiculite < Laponite < SWy-2 < Syn-1. The relative contribution of the protonated spectra is larger at 457.9 nm than at 488.0 nm, suggesting that the peak at 455 nm corresponds to the protonated species. In Laponite, the relative intensity of the meso substituent band at ∼1635 cm−1 indicates that the dihedral angle formed between the porphyrin and the methyl-pyridyl rings decreased in the non-protonated porphyrin as a consequence of intercalation. Raman data are thus consistent with the presence of at least two porphyrin species in resonance at 457.9 nm: the protonated and a more planar non-protonated porphyrin. At 488.0 nm the number of enhanced modes increases suggesting a decrease in the porphyrin symmetry. This allows assignment of the absorption band centered at 488 nm to a non-planar porphyrin conformation.
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Keywords: INTERCALATION; LAPONITE; MICA-SMECTITE SYN-1; MONTMORILLONITE SWY-2; PORPHYRIN; RAMAN SPECTROSCOPY; TETRAMETHYLPYRIDYLPORPHYRIN; TMPYP; UV-VISIBLE SPECTROSCOPY; VERMICULITE

Document Type: Research Article

Publication date: August 1, 2005

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  • The JOURNAL publishes articles of interest to the international community of clay scientists, including but not limited to areas in mineralogy, crystallography, geology, geochemistry, sedimentology, soil science, agronomy, physical chemistry, colloid chemistry, ceramics, petroleum engineering, foundry engineering, and soil mechanics. Clays and Clay Minerals exists to disseminate to its worldwide readership the most recent developments in all of these aspects of clay materials. Manuscripts are welcome from all countries.

    Clays and Clay Minerals is the official publication of The Clay Minerals Society.

    The Editor-in-Chief is Professor Joseph W. Stucki [email protected]

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