Abstract
The present study was undertaken to investigate the photophysical properties of the organic-metal compounds which are the main components of madder lake, one of the most commonly used and widespread organic pigments in painted artworks, from both geographic and historic points of view. Alizarin- and purpurin-Al(iii) complexes were studied in solution and as powders. In solution, the chelate stoichiometry, their absorption and emission properties and the efficiency of their excited electronic state deactivation pathways have been determined. The two organic-metal compounds show relevant differences in terms of spectral features consisting of multiple peak (structured) absorption and emission spectra for the purpurin derivative and single broad bands (structureless) for the Al(iii)-alizarin chelate. For both the investigated molecules, the chelation process induces a relevant increase of the emission quantum yields and lifetimes. The main differences between photophysical properties of the two metal complexes concern emission quantum yield and lifetime, which are both higher for purpurin chelate compared to alizarine chelate. Furthermore, interesting differences between the two metal complexes concerning the relative relevance of inter- and intra-molecular interaction involved in the mechanism of the excitation energy dissipation have been also highlighted. The knowledge of the determined parameters allows better understanding of the spectral behaviour in the solid state, thus providing a solid reference for the non-invasive characterisation and identification of madder lake on original artworks through its absorption and emission features.
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References
M. Picollo, M. Bacci, A. Casini, F. Lotti, S. Porcinai, B. Radicati, L. Stefani Martellucci et al. (ed.), Optical Sensors and Microsystems: New Concept, Materials, Technologies, Kluwer Academic/Plenum Publishers, New York, 2000.
M. Milazzo, G. Poldi, L. Bonizzoni, N. Ludwig and I. Mascheroni, Archaeometry, Proceedings of the 2004 International Archaeometry Symposium, Zaragoza, 2004.
M. J. Melo and A. Claro, Acc. Chem. Res., 2010, 43, 857.
A. Romani, C. Clementi, C. Miliani and G. Favaro, Acc. Chem. Res., 2010, 43, 837.
A. Nevin, D. Comelli, G. Valentini, D. Anglos, A. Burnstock, S. Cather and R. Cubeddu, Anal. Bioanal. Chem., 2007, 388, 1897.
M. Thoury, M. Elias, J. M. Frigerio and C. Barthou, Nondestructive Varnish Identification by Ultraviolet Fluorescence Spectroscopy, Appl. Spectrosc., 2007, 61, 1275.
R. Chenciner, Madder red: a history of luxury and trade, Curzon Press, London: Routledge, 2000.
M. Leona, Proc. Natl. Acad. Sci. U. S. A., 2009, 106, 15095.
J. Kirby, M. Spring and C. Higgitt, National Gallery Technical Bulletin, 2005, 26, 71.
C. Clementi, B. Doherty, P. L. Gentili, C. Miliani, A. Romani, B. G. Brunetti and A. Sgamellotti, Appl. Phys. A: Mater. Sci. Process., 2008, 92, 25.
D. Saunders and J. Kirby, National Gallery Technical Bulletin, 1994, 15, 79.
C. Clementi, W. Nowik, A. Romani, F. Cibin and G. Favaro, Anal. Chim. Acta, 2007, 596, 46.
V. Y. Fain, B. E. Zaitsev and M. A. Ryabov, Russ. J. Coord. Chem., 2004, 30, 365.
N. Komiha, O. K. Kabbaj and M. Charaibi, THEOCHEM, 2002, 594, 135.
C. H. Wunderlich and G. Bergerhoff, Chem. Ber., 1994, 127, 1185.
P. Soubayrol, G. Dana and P. P. Man, Magn. Reson. Chem., 1996, 34, 638.
M. Doskocz, K. Kubas, A. Frackowiak and R. Gancarz, Polyhedron, 2009, 28, 2201.
E. G. Kiel and P. M. Heertjes, J. Soc. Dyers Colour., 1963, 79, 21.
J. Sanyova, Contribution à l’éude de la structure et des propriétés des laques de Garance, PhD thesis, Bruxelles, 2000/2001.
J. Sanyova, Dyes in history and archaeology 21, edited by J. Kirby, Archetype publication, London 2008, ISBN: 9781904982074.
C. Miliani, A. Romani and G. Favaro, J. Phys. Org. Chem., 2000, 13, 141.
C. Miliani, A. Romani and G. Favaro, Spectrochim. Acta, Part A, 1998, 54, 581.
J. H. Yoe and A. L. Jones, Ind. Eng. Chem. Anal. Ed., 1944, 16, 111.
A. C. Boudet, J. P. Cornard and J. C. Merlin, Spectrochim. Acta, Part A, 2000, 56, 829.
J. P. Cornard and J. C. Merlin, J. Mol. Struct., 2003, 651–653, 381.
Recipe kindly provided by Jo Kirby (National Gallery of London).
P. Kubelka and F. Munk, Z. Tech. Phys., 1931, 12, 593.
C. Clementi, C. Miliani, G. Verri, S. Sotiropoulou, A. Romani, B. G. Brunetti and A. Sgamellotti, Appl. Spectrosc., 2009, 63, 1323.
G. Favaro, C. Clementi, A. Romani and V. Vickackaite, J. Fluoresc., 2007, 17, 707.
A. Claro, M. J. Melo, S. Schäfer, J. S. Seixas de Melo, F. Pina, K. Jan van den Berg and A. Burnstock, Talanta, 2008, 74, 9922.
G. B. Dutt and S. Doraiswamy, J. Chem. Phys., 1992, 96, 2475.
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Grazia, C., Clementi, C., Miliani, C. et al. Photophysical properties of alizarin and purpurin Al(III) complexes in solution and in solid state. Photochem Photobiol Sci 10, 1249–1254 (2011). https://doi.org/10.1039/c1pp05039g
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DOI: https://doi.org/10.1039/c1pp05039g