The influence of sulfonation degree (n) and central atom nature on singlet oxygen quantum yield (Φ_Δ) were studied for a series of sulfonated phthalocyanine metal complexes MPcS_n^mix. It was found that in DMSO, where the studied dyes exist as monomers, Φ_Δ values are independent of number and position of the sulfogroups and are equal to 0.11 ± 0.02, 0.19 ± 0.03, 0.37 ± 0.05, 0.38 ± 0.05 and 0.68 ± 0.10 for the metal-free and Mg, Gd, Al and Zn complexes, correspondingly. However, in aqueous solutions, aggregation of the dyes determines their photochemical activity. Substitution in adjacent to macrocycle 3 and 6 benzene positions interferes with aggregation compared to 4 and 5 positions, presumably due to enhanced steric hindrances in the former case. In the ZnPcS_n^mix series (n varied from 2 to 4), as an example, the linear relationship between degree of aggregation and Φ_Δ indicates that only the monomer fraction of the dye is responsible for singlet oxygen production. For less sulfonated samples the order of activity of the dyes in water is as follows: H₂PcS_n^mix < M^IIPcS_n^mix < M^IIIPcS_n^mix which is in contrast to their tendencies to form aggregates.

Keywords:

Most comprehensive & up-to-date research on PORPHYRINS
Handbook of Porphyrin Science now available in 46 volumes

References

R. Bonnett, Chem. Soc. Rev. 24, 19 (1995), DOI: 10.1039/cs9952400019. Crossref, Web of Science, Google Scholar
E. A. Lukyanets, J. Porphyrins Phthalocyanines 3, 424 (1999). Link, Web of Science, Google Scholar
N. A. Kuznetsova and O. L. Kaliya, Ross. Khim. Zh. 42, 36 (1998). Google Scholar
E. A. Luk'yanets, Ross. Khim. Zh. 42, 9 (1998). Web of Science, Google Scholar
V. V. Sokolovet al., Vop Onkol. 41, 134 (1995). Google Scholar
R. Edreiet al., J. Porphyrins Phthalocyanines 2, 191 (1998). Link, Web of Science, Google Scholar
P. C. Martinet al., Inorg. Chem. 30, 3305 (1991), DOI: 10.1021/ic00017a016. Crossref, Web of Science, Google Scholar
R. W. Boyle and D. Dolphin, Photochem. Photobiol. 64, 469 (1996), DOI: 10.1111/j.1751-1097.1996.tb03093.x. Crossref, Web of Science, Google Scholar
J. Moanet al., Photochem. Photobiol. 56, 171 (1992), DOI: 10.1111/j.1751-1097.1992.tb02144.x. Crossref, Web of Science, Google Scholar
H. L. L. M. van Leengoedet al., Photochem. Photobiol. 58, 575 (1993). Crossref, Web of Science, Google Scholar
D. Phillips, Prog. React. Kinet. Mech. 22, 175 (1997). Web of Science, Google Scholar
J. R. Wagneret al., Photochem. Photobiol. 45, 587 (1987), DOI: 10.1111/j.1751-1097.1987.tb07384.x. Crossref, Web of Science, Google Scholar
R. Gerdeset al., J. Photochem. Photobiol., A 111, 65 (1997), DOI: 10.1016/S1010-6030(97)00209-8. Crossref, Web of Science, Google Scholar
K. Lang, D. M. Wagnerova and J. Brodilova, J. Photochem. Photobiol., A 72, 9 (1993), DOI: 10.1016/1010-6030(93)85078-M. Crossref, Web of Science, Google Scholar
Amestica LA, Figueroa FR and Rojo JA. Chelant enhanced photobleaching and laundry detergent compositions; US Patent 5972038, 1999 . Google Scholar
Willey AD, Jeffreys B, Ingram DW and Harriman A. Photochemical singlet oxygen generators having enhanced singlet oxygen yields for bleaching agents; WO Patent 9832825, 1998 . Google Scholar
N. A. Kuznetsovaet al., Russ. J. Gen. Chem. 71, 36 (2001), DOI: 10.1023/A:1012369120376. Crossref, Web of Science, Google Scholar
J. H. Weber and D. H. Busch, Inorg. Chem. 4, 469 (1965), DOI: 10.1021/ic50026a007. Crossref, Web of Science, Google Scholar
I. S. Ioffe and N. I. Devyatova, Zh. Obshch. Khim. 32, 2111 (1962). Google Scholar
F. H. Moser and A. L. Thomas, The Phthalocyanines 2 (CRC Press, Boca Raton, FL, 1983) p. 20. Google Scholar
V. M. Derkachevaet al., First International Conference on Porphyrins and Phthalocyanines (2000) p. 389. Google Scholar
S. M. Bishopet al., J. Chromatogr., A 646, 345 (1993), DOI: 10.1016/0021-9673(93)83347-U. Crossref, Web of Science, Google Scholar
J. M. Fernandez, M. D. Bilgin and L. I. Grossweiner, J. Photochem. Photobiol., B 37, 131 (1997), DOI: 10.1016/S1011-1344(96)07349-6. Crossref, Web of Science, Google Scholar
N. A. Kuznetsovaet al., Russ. J. Gen. Chem. 70, 140 (2000). Web of Science, Google Scholar
W. Spilleret al., J. Porphyrins Phthalocyanines 2, 145 (1998). Link, Web of Science, Google Scholar
I. Rosenthalet al., Radiat. Res. 107, 136 (1986), DOI: 10.2307/3576857. Crossref, Web of Science, Google Scholar
J. Kraska and W. Czajkowski, Rocz. Chem. 50, 845 (1976). Google Scholar
E. N. Fedorovaet al., Trudy Ivanovskogo KhTI 20, 70 (1976). Google Scholar
R. B. Ostleret al., Photochem. Photobiol. 71, 397 (2000). Crossref, Web of Science, Google Scholar
D. Phillips, Pure Appl. Chem. 67, 117 (1995), DOI: 10.1351/pac199567010117. Crossref, Web of Science, Google Scholar
T. Reinotet al., Chem. Phys. Lett. 299, 410 (1999), DOI: 10.1016/S0009-2614(98)01346-3. Crossref, Web of Science, Google Scholar
M. Sekota and T. Nyokong, Polyhedron 16, 3279 (1997), DOI: 10.1016/S0277-5387(97)00096-X. Crossref, Web of Science, Google Scholar
I. McCubbin and D. Phillips, J. Photochem. 34, 187 (1986), DOI: 10.1016/0047-2670(86)85018-3. Crossref, Web of Science, Google Scholar
J. D. Spikes, J. E. van Lier and J. C. Bommer, J. Photochem. Photobiol., A 91, 193 (1995), DOI: 10.1016/1010-6030(95)04129-3. Crossref, Web of Science, Google Scholar
M. E. Daraioet al., Photochem. Photobiol. 54, 367 (1991), DOI: 10.1111/j.1751-1097.1991.tb02029.x. Crossref, Web of Science, Google Scholar
G. Valdugaet al., J. Photochem. Photobiol. 48, 1 (1988). Crossref, Web of Science, Google Scholar