ꢁ
observation of the kinetic formation of Py2 þ(SAꢀ)2/(bCD)2
5
R. Goedeweeck, M. Vanderauweraer and F. C. Deschryver,
J. Am. Chem. Soc., 1985, 107, 2334.
C. Garcia-Echeverria, J. Am. Chem. Soc., 1994, 116, 6031.
J. T. Richards, G. West and J. K. Thomas, J. Phys. Chem., 1970,
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A. Kira, M. Imamura and T. Shida, J. Phys. Chem., 1976, 80,
1445.
A. Kira and M. Imamura, J. Phys. Chem., 1979, 83, 2267.
from the dimerization of PyꢁþSAꢀ/bCD and PySAꢀ/bCD.
There are possibilities of the kinetic formation of Py2 and
ꢁ
þ
6
7
ꢁ
Py2 þ(SAꢀ)2 as a kinetic probe of the environment of the Py
chromophore.
8
9
10 S. Neumann, R. Korenstein, Y. Barenholz and M. Ottolenghi, Isr.
J. Chem., 1982, 22, 125.
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13 A. Kira, S. Arai and M. Imamura, J. Chem. Phys., 1971, 54, 4890.
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15 M. A. J. Rodgers, Chem. Phys. Lett., 1971, 9, 107.
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17 A. Tsuchida, T. Ikawa, M. Yamamoto, A. Ishida and S.
Takamuku, J. Phys. Chem., 1995, 99, 14 793.
18 C. Bohne, E. B. Abuin and J. C. Scaiano, J. Am. Chem. Soc.,
1990, 112, 4226.
19 Y. Barenholz, T. Cohen, R. Korenstein and M. Ottolenghi,
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chemistry, Marcel Dekker, New York, 2nd edn., 1992.
21 M. A. J. Rodgers, J. Chem. Soc., Faraday Trans. 1, 1972, 68, 1278.
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26 J. W. Steed and J. L. Atwood, Supramolecular chemistry,
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27 T. Yorozu, M. Hoshino, M. Imamura and H. Shizuka, J. Phys.
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28 K. Kano, I. Takanoshita and T. Ogawa, J. Phys. Chem., 1982,
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31 E. Blatt, A. Launikonis, A. W. H. Mau and W. H. F. Sasse, Aust.
J. Chem., 1987, 40, 1.
Conclusions
ꢁ
ꢁ
ꢁ
þ
þ
Formation and decay of Py
, , and
Py þSAꢀ, Py2
ꢁ
Py2 þ(SAꢀ)2 during the 355-nm TPI of Py and sodium PySAꢀ
in the absence and presence of cyclodextrins were investigated
with the transient absorption measurement concerning the sol-
vent effect and environment effect of the inclusion compounds
of PySAꢀ in CD. Formation and decay of Pyꢁþ, PyꢁþSAꢀ,
ꢁ
ꢁ
Py2 þ, and Py2 þ(SAꢀ)2 are discussed based on the LE band
ꢁ
ꢁ
of the radical cations (Py and Py þSAꢀ) and dimer radical
þ
ꢁ
ꢁ
þ
catiꢁons (Py2 and Py2 þ(SAꢀ)2) as well as the CR band of
ꢁ
ꢁ
þ
þ
Py2 and Py2 þ(SAꢀ)2 . Formation of Py was observed in
polar solventsꢁbut not in CH because of the fast charge recom-
ꢁ
þ
þ
bination. Py2 formed from dimerization of Py and Py
ꢁ
(3.0 ꢂ 10ꢀ3 M) with t1/2 of 51 ns in DCE. Py2 þ(SAꢀ)2 formed
from dimerization of PyꢁþSAꢀ and PySAꢀ (2.7 ꢂ 10ꢀ4 M) with
ꢁ
t
1/2 of 1.4 ms in D2O. On the other hand, Py2 þ(SAꢀ)2/(bCD)2
ꢁ
with PO and FO structures of Py2 þ in the cavity of two bCDs
formed with t1/2 of 1.8 ms at [PySAꢀ] ¼ 2.7 ꢂ 10ꢀ4 M and
ꢁ
[bCD] ¼ 10ꢀ2 M. Py2 þ(SAꢀ)2/(gCD)2 with FO structure of
ꢁ
þ
Py2 formed immediately after the laser flash. The PO and
FO structures were identified by the characteristic CR bands
around 1500 aꢁnd 1700 nm, respectively. It should be empha-
sized that Py2 þ(SAꢀ)2/(bCD)2 forms from dimerization of
PyꢁþSAꢀ/bCD and PySAꢀ/bCD, while Py2 þ(SAꢀ)2/(gCD)2
ꢁ
forms directly from the TPI of (PySAꢀ)2 in (PySAꢀ)2/
(gCD)2 . This is explained by the existence of PySAꢀ/bCD
and (PySAꢀ)2/(gCD)2 in the ground state. One Py chromo-
phore exists in the cavity of bCD, while two Py chromophores
exist with the parallel configuration in the cavity of two gCDs.
ꢁ
The neutralization of Py2 þ(SAꢀ)2 is inhibited in the cꢁavities of
bCD and gCD. No exclusion of PyꢁþSAꢀ and Py2 þ(SAꢀ)2
occurs from the cavities of CD.
32 E. Blatt, Aust. J. Chem., 1987, 40, 851.
33 K. Kano, H. Matsumoto, S. Hashimoto, M. Sisido and Y.
Imanishi, J. Am. Chem. Soc., 1985, 107, 6117.
34 H. Kobashi, M. Takahashi, Y. Muramatsu and T. Morita, Bull.
Chem. Soc. Jpn., 1981, 54, 2815.
Acknowledgements
This work has been partly supported by a Grant-in-Aid for
Scientific Research on Priority Area (417), 21st Century
COE Research, and others from the Ministry of Education,
Culture, Sports, Science and Technology (MEXT) of the
Japanese Government.
35 A. Harada and S. Nozakura, Polym. Bull. (Berlin), 1982, 8, 141.
36 S. Hamai, J. Phys. Chem., 1988, 92, 6140.
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39 H. M. Rosenstock, K. Draxl, B. W. Steiner and J. J. Herron,
J. Phys. Chem. Ref. Data, 1977, 6, Supplement No. 1.
40 CRC Handbook of Radiation Chemistry, ed. Y. Tabata, Y. Ito and
S. Tagawa, CRC Press, Boca Raton FL, 1991.
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T h i s j o u r n a l i s Q T h e O w n e r S o c i e t i e s 2 0 0 4
3220
P h y s . C h e m . C h e m . P h y s . , 2 0 0 4 , 6 , 3 2 1 5 – 3 2 2 0