K. Kano et al.
Bull. Chem. Soc. Jpn., 76, No. 10 (2003) 2033
24
benzoates and the K values. Meanwhile, a rough linear rela-
tionship exists between the K values for complexation of the
para-substituted benzoates having the electron-withdrawing
groups and the Hammett’s ꢁ values. Our results are consistent
References
For a review: H.-J. Schneider, L. Tianjun, M. Sirish, and V.
Malinovski, Tetrahedron, 58, 779 (2002).
1
2
1994).
3
H.-J. Schneider and M. Wang, J. Org. Chem., 59, 7464
12
with those obtained by Cozzi et al. However, the results that
the benzoate anion without any substituent and the p-methyl-
and p-methoxybenzoate anions do not interact with ZnTPPS
are hardly explained by a simple polar effect. Although the de-
tailed mechanism for the interaction between ZnTPPS and
mono-substituted benzoate anions has not been clarified, it
may be concluded that the electron-withdrawing groups in
the benzoates diminish the ꢀ–ꢀ repulsive interaction to make
the London dispersion force effective for stacking. The van’t
(
K. Kano, T. Sato, S. Yamada, and T. Ogawa, J. Phys.
Chem., 87, 566 (1983).
4
1984).
5
T. Sato, T. Ogawa, and K. Kano, J. Phys. Chem., 88, 3678
(
K. Kano, T. Nakajima, and S. Hashimoto, J. Phys. Chem.,
9
1, 6614 (1987).
C. A. Hunter and J. K. M. Sanders, J. Am. Chem. Soc., 112,
5525 (1990).
6
0
Hoff plot provided the enthalpy (ÁH ) and entropy changes
0
7 K. Kano, K. Fukuda, H. Wakami, R. Nishiyabu, and R. F.
Pasternack, J. Am. Chem. Soc., 122, 7494 (2000).
8 W. L. Jorgensen and D. L. Severance, J. Am. Chem. Soc.,
112, 4768 (1990).
(
ÁS ) for the association of the p-cyanobenzoate anion and
À1
ZnTPPS to be À27:6 Æ 2:4 kJ mol
and À53:5 Æ 8:0
À1 À1
25
K , respectively. These thermodynamic parameters
J mol
9
H. Stamm, H.-D. Strumm, K.-H. Loebel, H. J a¨ ckel, U.
suggest the van der Waals interaction to be the main binding
force as previously discussed for the complexation of the cat-
ionic porphyrin free bases with p-benzoquinone.
1H NMR data suggest the structure of the ZnTPPS–AQS
complex as shown in Fig. 4a. In order to avoid a steric hin-
drance due to the sulfonatophenyl groups at the meso-positions
of ZnTPPS, the AQS molecule should tilt against the porphy-
rin plane. In such a structure, the stacking interaction of
ZnTPPS mainly occurs with hydrophobic ring B. There are
two possible arrangements for the tilted arrangement, the
face-to-face type and the T-shape type (see Fig. 4). We could
not verify which arrangement is more stable.
Hoffmanns, S. Bethke, and G. Schilling, J. Chem. Soc., Perkin
Trans. 2, 2001, 2089.
26
10
Tanabe, J. Am. Chem. Soc., 124, 104 (2002).
M. Enescu, N. Levy, and V. Cheorghe, J. Phys. Chem.,
04, 1073 (2000).
a) F. Cozzi, M. Cinquini, R. Annunziata, and J. S. Siegel, J.
S. Tsuzuki, K. Honda, T. Uchimaru, M. Mikami, and K.
1
1
1
1
2
Am. Chem. Soc., 114, 5729 (1992). b) F. Cozzi and J. S. Siegel,
Pure Appl. Chem., 67, 683 (1995).
1
3
D. G. Hamilton, J. E. Davis, L. Prodi, and J. K. M. Sanders,
Chem.—Eur. J., 4, 608 (1998).
G. J. Gabriel and B. L. Iverson, J. Am. Chem. Soc., 124,
5174 (2002).
K. Kano, H. Hasegawa, and M. Miyamura, Chirality, 13,
74 (2001).
B. W. Bangerter and S. I. Chan, J. Am. Chem. Soc., 91,
910 (1969).
For leading papers: a) O. Ohno, Y. Kaizu, and H.
1
4
As a consequence, the present study suggests the important
contribution of the polar effect to stacking interactions be-
tween aromatic molecules, which have been demonstrated by
1
4
3
1
5
4
12
Kano et al. and Cozzi et al.
1
6
1
7
Experimental
Kobayashi, J. Chem. Phys., 99, 4128 (1993). b) J. M. Ribo, J.
Crusats, J. A. Farrera, and M. L. Valero, J. Chem. Soc., Chem.
Commun., 1994, 681. c) N. C. Maiti, S. Mazumdar, and P. N.
Shyamalava, J. Phys. Chem. B, 102, 1528 (1998). d) J. Parkash,
J. H. Robblee, J. Agnew, E. Gibbs, P. Collings, R. F. Pasternack,
and J. C. de Paula, Biophys. J., 74, 2089 (1998). e) N. Micali, F.
Mallamace, A. Romeo, R. Purrello, and L. Monsu Scolaro, J.
Phys. Chem. B, 104, 5897 (2000).
ZnTPPS was prepared by reacting TPPS (Tokyo Kasei, –SO3H
27
form) with zinc oxide in boiling water. After the reaction, the
reaction mixture was filtered using a membrane filter, and the fil-
trate was passed through an ion-exchange region column (DOW-
EX HCR-W2, 20–50 mesh) to obtain Na salt. ZnTPPS in water
TM
was purified by gel-filtration (Sephadex G-25 Fine). An ele-
mental analysis indicated the formation of ZnTPPS 7H2O. Anal.
ꢂ
Calcd for C44H26N4Na4O12S4Zn 7H2O: C43.52; H, 3.32; N,
ꢂ
18 A. Mishra, R. K. Behera, P. K. Behera, B. K. Mishra, and
G. B. Behera, Chem. Rev., 100, 1973 (2000).
4
was prepared by the reduction of AQS sodium salt (Nacalai) with
.61%; found: C, 43.02, H, 3.17; N, 4.35%. The AS sodium salt
1
9
K. Kano, R. Nishiyabu, T. Asada, and Y. Kuroda, J. Am.
Chem. Soc., 124, 9937 (2002).
a) B. C. Burdett, ‘‘Aggregation Processes in Solution,’’ ed
28
zinc powder in 28% aqueous ammonia. The reaction mixture
was filtered and the filtrate was treated with active carbon. Crude
AS was repeatedly recrystallized from water. The AQDS disodi-
um salt purchased from Tokyo Kasei was recrystallized from
water. The benzoic acids (reagent grades) were purchased and
used without further purification.
2
0
by E. Wyn-Jones and J. Gormally, Elsevier Scientific Publishing,
Amsterdam (1983), pp. 241–270. b) V. Vitagliano, ‘‘Aggregation
Processes in Solution,’’ ed by E. Wyn-Jones and J. Gormally,
Elsevier Scientific Publishing, Amsterdam (1983), pp. 271–308.
The absorption spectra were measured on a Shimadzu UV-2100
1
2
1E.-i. Kim, S. Paliwal, and C. S. Wilcox, J. Am. Chem. Soc.,
20, 11193 (1998).
S. R. S. Iyer and G. S. Singh, J. Soc. Dyers Colour., 89,
28 (1973).
C. A. Mattia, L. Mazzarella, V. Vitagliano, and R. Puliti, J.
spectrophotometer. The H NMR spectra (400 MHz) were taken
on a JEOL GX-400 spectrometer using 3-trimethylsilyl[2,2,3,3-
d4]propionate (TSP, Aldrich) as an external standard.
1
2
2
1
2
3
This work was supported by a Grand-in-Aid for Scientific
Research B (KAKENHI 14340224) from the Ministry of Edu-
cation, Culture, Sports, Science and Technology.
Crystallogr. Spectrosc. Res., 14, 71( 19 84).
24 K. L. Miller and J. A. Savchik, J. Am. Chem. Soc., 101,
7206 (1988).