T. Hayashi, H. Ogoshi et al.
FULL PAPER
150.39 ± 150.88, 154.39 ± 154.80; MS-FAB : 1245 [M ]; HRMS-FAB : calcd
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for C80H100N4O464Zn [M ] 1244.7036, found 1244.6968.
meso-Tetrakis(2-hydroxy-4-nonylphenyl)porphyrin nickel(II) complex (1 ´
Ni): A solution of Ni(OAc)2 ´ 4H2O (48 mg, 0.19 mmol) in MeOH (4 mL)
was added to a solution of 1 (90 mg, 0.076 mmol) in CHCl3 (20 mL). The
mixture was refluxed for 45 min, cooled to room temperature, and poured
into H2O. The organic layer was separated and the aqueous layer was
extracted with Et2O. The combined organic layer was washed with H2O and
dried over anhydrous Na2SO4. The solution was filtered and concentrated
under reduced pressure to give 90 mg (0.073 mmol, 92%) of 1 ´ Ni. 1H
NMR spectroscopy of a mixture of the four atropisomers (500 MHz,
CDCl3): d 0.906 (t, J 7.0 Hz, 12H), 1.26 ± 1.64 (m, 48H), 1.81 ± 1.89 (m,
8H), 2.83 ± 2.86 (m, 8H), 4.72, 4.73, 4.74, 4.75, 4.77, 4.77 (s, total 4H), 7.07 ±
[5] Recently, we have reported that meso-tetrakis(2-hydroxynaphthyl)-
porphyrin (2) is a suitable ubiquinone receptor. The atropisomeriza-
tion of 2 was not detected even in boiling toluene. T. Hayashi, T.
Miyahara, N. Koide, Y. Kato, H. Masuda, H. Ogoshi, J. Am. Chem.
Soc. 1997, 119, 7281.
[6] T. Hayashi, T. Asai, H. Hokazono, H. Ogoshi, J. Am. Chem. Soc. 1993,
115, 12210.
[7] L. K. Gottwald, E. F. Ullman, Tetrahedron Lett. 1969, 3071.
[8] C. M. Elliott, Anal. Chem. 1980, 52, 666.
7.13 (m, 8H), 7.64 ± 7.68 (a mixture of doublets, total 4H), 8.81 (s, 8H); 13
C
NMR spectroscopy of a mixture of the four atropisomers (125 MHz,
CDCl3):[26] d 14.18, 22.78, 29.47, 29.64, 29.70, 29.72, 31.35, 32.01, 36.08,
113.56 ± 113.98, 114.07 ± 114.95, 119.71 ± 119.82, 124.91 ± 125.36, 132.06 ±
132.46, 134.51 ± 134.87, 145.19 ± 145.62, 150.24 ± 150.85, 153.38 ± 154.75;
MS-FAB : 1239 [M ]; HRMS-FAB : calcd for C80H100N4O458Ni [M ]
[9] J. Lindsey, J. Org. Chem. 1980, 45, 5215.
1238.7098, found 1238.7114.
[10] Several groups have described a thermal shift in the equilibrium of
atropisomers at high temperatures. See for example: a) N. Nishino, K.
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Binding studies: All UV/visible binding studies were carried out on a
Hewlett ± Packard 8452A diode array spectrophotometer with CHCl3
containing 2-methyl-2-butene as a stabilizer. Initially, a porphyrin solution
(2.0 mL, [porphyrin] 10 5 ± 10 4 m) was poured into a 1 cm quartz cell.
The UV/visible spectrum of the pure host solution was recorded, and some
of the stock quinone solution (e.g. 10 mL) was transferred into the cell with
a syringe. The spectrum was recorded and the process was repeated until
the desired guest-to-host ratio was obtained. The parameters from the
changes in monitored absorbance were calculated using a nonlinear curve-
fitting procedure based on the damped Gauss ± Newton method.
Á
Quelquejeu, N. Bernard, A. Kossanyi, B. Desmazieres, J. Org. Chem.
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[13] The rate constant for internal rotation about the C(aryl) ± C(por-
phyrin) bond in Ullmanꢁs porphyrin, meso-tetrakis(2-hydroxyphe-
Determination of the relative amounts of each atropisomer: All NMR
spectroscopy studies were carried out on a JEOL A-500 NMR spectrom-
eter using CDCl3 without further purification. A solution of porphyrin and
quinone was placed in a 5 mm NMR spectroscopy tube under Ar and
sealed. The tube was maintained in a bath held at constant temperature ( Æ
18C) and measurements were taken at regular time intervals.
1
nyl)porphyrin, is 1.5 Æ 0.5 Â 10 5 s in methanol at 238C.[7]
[14] In the previous paper, association constants were determined in
chloroform containing trace amounts of ethanol as a stabilizer.[6]
However, ethanol can act as a competitive inhibitor in the formation
of hydrogen-bonded complexes. In this paper, we used chloroform
containing 2-methyl-2-butene as a stabilizer to obtain the thermody-
namic parameters.
Acknowledgements: This work was supported by a Grant-in-Aid of
Specially Promoted Research (No. 04101003) from the Ministry of
Education, Science, and Culture (Japan). F.M.B. (Johannes Gutenberg
University, Mainz) gratefully acknowledges financial support from the
Deutscher Akademischer Austauschdienst (DAAD) under the program
for Integrated Studies Abroad, during his stay at Kyoto University in
1993 ± 1994. T.H. thanks Prof. Y. Hisaeda from Kyushu University for his
warm encouragement during the preparation of this article.
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corresponding with the host porphyrin is a measure of the total
concentration of ([1aaaa] [1aaaa ± Q]) and ([1aaab] [1aaab ± Q]), re-
spectively, since the exchange process between the free and com-
plexed host molecule is fast on the NMR time scale.
Received: January 7, 1998 [F953]
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in Figure 8 and 11.
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atropisomers.
a mixture of four
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