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H. Isago et al. / Dyes and Pigments 88 (2011) 187e194
that of Q-band is understandable if the assignment is correct,
because it is known that scattering of plots for Soret band is more
significant than those for Q-band in solvatochromism of metal-free
porphyrins [49]. This is because the Q-band of Pcs is an essentially
pure monoelectonic transition while the Soret band is a mixture of
a few transitions with comparable ratios [4]. In addition to that, we
have reported that the solvent-dependence of B1/B2 bands is much
more significant than that of Q-band for [Sb(pc)(OH)2]þ [14].
The solvatochromic behavior of the n-butoxyl-substituted
derivative is more rigorous than those of the tppc analogues
because of the presence of more or less aggregation effects (as
mentioned above). It is well known that susceptibility to aggrega-
tion depends on the nature of the solvent system [50,51]. The much
more scattered plots for tObpc derivative than the tppc analogues
may be rationalized as follows. Aggregation of Pc macrocycles
generally gives rise to a significant spectral change, like blue-/red-
shift, broadening, or splitting of the absorption band, as mentioned
above. In particular, as the extra band is considerably broadened
unlike the well-isolated Q-band, presence of any small portion of
aggregated species can shift the absorption maximum wavelength.
Eventually, Fig. 7 shows considerably scattered plots for tObpc
derivative with respect to the extra band.
References
[1] Leznoff CC, Lever ABP, editors. Phthalocyanines, properties and applications.
New York: VCH Publications; 1989 for vol. 1, 1993 for vol. 2, 1993 for vol. 3,
and 1996 for vol. 4.
[2] Shirai H, Kobayashi N, editors. Phthalocyanines: chemistry and functions.
Tokyo: IPC Publishers; 1997 [in Japanese].
[3] Cid J-J, Yun J-H, Jang S-R, Nazeeruddin MK, Martinez-Ferrero E, Palomares E,
et al. Angew Chem 2007;119:8510e4.
[4] Stillman MJ, Nyokong T. In: Leznoff CC, Lever ABP, editors. Phthalocyanines,
properties and applications, vol. 1. New York: VCH Publications; 1989. p. 133e290.
[5] Isago H. In: Hirohashi R, Sakamoto K, Okumura E, editors. Phthalocyanines as
functional dyes. Tokyo: IPC Publishers; 2004. p. 141e98 [in Japanese].
[6] Nyokong T, Isago H. J Porph Phthal 2004;8:1083e90.
[7] Fukuda T, Ono K, Homma S, Kobayashi N. Chem Lett 2003;32:736e7.
[8] Kobayashi N, Fukuda T, Ueno K, Ogino H. J Am Chem Soc 2001;123:10740e1.
[9] Kagaya Y, Isago H. Chem Lett; 1994:1957e60.
[10] Isago H, Kagaya Y, Nakajima Sei. Chem Lett 2003;32:112e3.
[11] Isago H. Chem Commun; 2003:1864e5.
[12] Isago H, Kagaya Y, Matsushita A. Chem Lett 2004;33:862e3.
[13] Zahir Md H, Kagaya Y, Isago H, Furubayashi T. Inorg Chim Acta 2004;357:2755e8.
[14] Isago H, Kagaya Y. J Porph Phthal 2009;13:382e9.
[15] Isago H, Kagaya Y. Chem Lett 2006;35:8e9.
[16] Isago H, Miura K, Oyama Y. J Inorg Biochem 2007;102:380e7.
[17] Isago H, Miura K, Kanesato M. J Photochem Photobiol 2008;197:313e20.
[18] Isago H, Kagaya Y. Bull Chem Soc Jpn 1996;69:1281e8.
[19] Kagaya Y, Isago H. Bull Chem Soc Jpn 1997;70:2179e85.
[20] Gasyna Z, Kobayashi N, Stillman MJ. J Chem Soc Dalton Trans; 1989:2397e405.
[21] Modibane DK, Nyokong T. Polyhedron 2009;28:479e84.
[22] Tempone AG, Perez D, Rhat S, Vilarinho AL, Mortara RA, de Andrade Jr HF.
J Antimicrob Chemother 2004;54:60e8.
[23] Blum J, Desjeux P, Schwartz E, Beck B, Hatz C. J Antimicrob Chemother
2004;53:158e66.
4. Conclusions
[24] Ashutosh, Sunder S, Goyal N. J Med Microbiol 2007;56:143e53.
[25] Isago H, Leznoff CC, Ryan MF, Metcalfe RA, Davids R, Lever ABP. Bull Chem Soc
Jpn 1998;71:1039e47.
Three novel antimony(V) phthalocyanines that show an amber
color have been synthesized by cyclic tetramerization of alkoxyl-
and phenoxyl-substituted phthalonitrile in the presence of SbI3 and
then by oxidizing the produced antimony(III)-Pcs with tert-butyl
perbenzoate or sulfuryl chloride through an oxidative addition
process. They show an amber color in solution unlike normal Pcs.
Their non-blue coloration is attributable to a significant red-shift
of the Q-band and appearance of a new broad band around
400e500 nm (where normal Pcs do not absorb light). MCD and
solvent-dependence study on the extra band have suggested that
this band should be significantly red-shifted Soret (B1/B2) band.
[26] Isago H, Terekhov DS, Leznoff CC. J Porph Phthal 1997;1:135e40.
[27] Terekhov DS, Nolan KJM, McArthur CR, Leznoff CC. J Org Chem 1996;61:3034e40.
[28] Nevin WA, Liu W, Lever ABP. Can J Chem 1987;65:855e8.
[29] Monahan AR, Brado JA, Deluca AF. J Phys Chem 1972;73:1994e6.
[30] Monahan AR, Brado JA, Deluca AF. J Phys Chem 1972;76:446e9.
[31] Abkowitz M, Monahan AR. J Chem Phys 1973;58:2281e7.
[32] Kasha M, Rawls HR, El-Bayoumi MA. Pure Appl Chem 1965;11:371e92.
[33] Simon J, Bassoul P. In: Leznoff CC, Lever ABP, editors. Phthalocyanines, prop-
erties and applications, vol. 2. New York: VCH Publications; 1993. p. 223e99.
[34] Volger A, Nikol H. Pure Appl Chem 1992;64:1311e7.
[35] Edwards L, Gouterman M. J Mol Spectrosc 1970;33:292e310.
[36] Nyokong T, Gasyna Z, Stillman MJ. Inorg Chem 1987;26:1087e95.
[37] Ough E, Nyokong T, Creber KAM, Stillman MJ. Inorg Chem 1988;27:2724e32.
[38] Hollebone BR, Stillman MJ. J Chem Soc Faraday Trans II 1978;74:2107e27.
[39] Van Cott TC, Rose JL, Misener GC, Williamson BE, Schrimp AE, Boyle ME, et al.
J Phys Chem 1989;93:2999e3011.
Acknowledgements
[40] Stillman MJ. In: Leznoff CC, Lever ABP, editors. Phthalocyanines, properties
and Applications, vol. 3. New York: VCH Publications; 1993. p. 231e96.
[41] Yamamoto A, Phillips LK, Calvin M. Inorg Chem 1968;7:847e52.
[42] Wilshire J, Lever ABP, Unpublished Data (shown as Figure 33 in Ref. 4).
[43] Stillman MJ, Thomson AJ. J Chem Soc Faraday Trans II 1974;70:790e804.
[44] Isago H. J Porph Phthal 2006;10:1125e31.
The authors (HI and TS) are grateful to Prof. Masahiko Inouye
(Univ. of Toyama) for his generosity and willingness to let us use the
mass spectrometers for our purpose. This work was supported in
part by a grant from Japan Society for the Promotion of Science
(KAKENHI; No. 20550170).
[45] Crack DW, Yandle JR. Inorg Chem 1971;11:1738e42.
[46] Kobayashi N, Ogata H, Nonaka N, Luk’yanets EA. Chem Eur J 2003;9:5123e34.
[47] Kobayashi N, Sasaki N, Higashi Y, Osa T. Inorg Chem 1995;34:1636e7.
[48] Suppan P. J Photochem Photobiol Sect A 1990;50:293e330.
[49] Tran-Thi TH, Lipskier JF, Maillard P, Momenteau M, Lopez-Cassilo JeM, Jay-
Gerin JeP. J Phys Chem 1992;96:1073e82.
Appendix. Supplementary data
[50] Kobayashi N, Lever ABP. J Am Chem Soc 1987;109:7433e41.
[51] Sielcken OtE, van Tillborg MM, Roks MFM, Hendricks R, Drenth W, Nolte RJM.
J Am Chem Soc 1987;109:4261e5.
Supplementary data associated with this article can be found in