Helicity induction and conformational dynamics of poly(bis(4-carboxyphenoxy)phosphazene) with optically active amines [2]

Journal of the American Chemical Society

Volumn 122, Issue 32, 2000, Pages 7813-7814

  Yashima, Eiji ^a,b   Maeda, Katsuhiro ^a   Yamanaka, Toshio ^a  

^a NAGOYA UNIVERSITY   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; POLYMER;

CIS TRANS ISOMERISM; CONFORMATION; CONFORMATIONAL TRANSITION; LETTER; OPTICAL ROTATION; RACEMIC MIXTURE; X RAY DIFFRACTION;

EID: 0034674970     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja994156e     Document Type: Letter

References (44)

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29. We tried to estimate the thermodynamic parameters for this process using the standard Arrhenius analysis, but it was difficult due to the nonlinear relation between the kinetics and temperature.
30. Recently, Novak et al. reported a similar, but irreversible transformation for an optically inactive polyguanidine complexed with optically active camphorsulfonic acid. Schlitzer, D. S.; Novak, B. M. J. Am. Chem. Soc. 1998, 120, 2196-2197.
31. The net specific rotation of the CT - (R)-2 complex is almost exactly the same as that of pure (R)-2. (14) Similar helicity induction through chiral interactions has been observed for other optically inactive polymers, see ref 12. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801. Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359. Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600. (e) Yashima, E.; Goto, H.; Okamoto, Y. Polym. J. 1998, 30, 69-71. (f) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926. (g) Norris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
32. The net specific rotation of the CT - (R)-2 complex is almost exactly the same as that of pure (R)-2. (14) Similar helicity induction through chiral interactions has been observed for other optically inactive polymers, see ref 12. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801. Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359. Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600. (e) Yashima, E.; Goto, H.; Okamoto, Y. Polym. J. 1998, 30, 69-71. (f) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926. (g) Norris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
33. The net specific rotation of the CT - (R)-2 complex is almost exactly the same as that of pure (R)-2. (14) Similar helicity induction through chiral interactions has been observed for other optically inactive polymers, see ref 12. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801. Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359. Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600. (e) Yashima, E.; Goto, H.; Okamoto, Y. Polym. J. 1998, 30, 69-71. (f) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926. (g) Norris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
34. The net specific rotation of the CT - (R)-2 complex is almost exactly the same as that of pure (R)-2. (14) Similar helicity induction through chiral interactions has been observed for other optically inactive polymers, see ref 12. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801. Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359. Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600. (e) Yashima, E.; Goto, H.; Okamoto, Y. Polym. J. 1998, 30, 69-71. (f) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926. (g) Norris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
35. The net specific rotation of the CT - (R)-2 complex is almost exactly the same as that of pure (R)-2. (14) Similar helicity induction through chiral interactions has been observed for other optically inactive polymers, see ref 12. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801. Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359. Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600. (e) Yashima, E.; Goto, H.; Okamoto, Y. Polym. J. 1998, 30, 69-71. (f) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926. (g) Norris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
36. The net specific rotation of the CT - (R)-2 complex is almost exactly the same as that of pure (R)-2. (14) Similar helicity induction through chiral interactions has been observed for other optically inactive polymers, see ref 12. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801. Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359. Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600. (e) Yashima, E.; Goto, H.; Okamoto, Y. Polym. J. 1998, 30, 69-71. (f) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926. (g) Norris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
37. The net specific rotation of the CT - (R)-2 complex is almost exactly the same as that of pure (R)-2. (14) Similar helicity induction through chiral interactions has been observed for other optically inactive polymers, see ref 12. (a) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995, 117, 11596-11597. (b) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1996, 118, 9800-9801. Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1997, 119, 6345-6359. Yashima, E.; Maeda, Y.; Matsushima, T.; Okamoto, Y. Chirality 1997, 9, 593-600. (e) Yashima, E.; Goto, H.; Okamoto, Y. Polym. J. 1998, 30, 69-71. (f) Maeda, K.; Yamamoto, N.; Okamoto, Y. Macromolecules 1998, 31, 5924-5926. (g) Norris, I. D.; Kane-Maguire, L. A. P.; Wallace, G. G. Macromolecules 1998, 31, 6529-6533.
38. 4b may be specific to the induced helical conformation of the poly-1 - (R)-2 complex.
39. Preliminary viscosity measurements were conducted for the poly-1 -(R)-2 complex ([poly-1] = 0.5 g/dL, [(R)-2]/[carboxy residues of poly-1] = 5). The viscosity gradually increased with time. However, once the solution was annealed at 65°C for 2 h, the viscosity significantly decreased accompanying an increase in the specific rotation, and the viscosity and rotation values did not change further with time. These results indicate that poly-1 may intermolecularly interact to form a kind of aggregates before annealing. However, once it is annealed in the initial stage or later, the polymer may disaggregate to form an intramolecularly stable conformation, probably a helical conformation, thus showing a large negative optical rotation. Once it's happened, no aggregation may occur so that the viscosity and optical rotation remain unchanged. When the poly-1 - (R)-2 solution was further annealed at higher temperatures (>80°C), the induced helical conformation of poly-1 may partially collapse and the optical rotation decreases. However, after further annealing the sample at 65°C for 2 h again, the polymer forms a helical conformation and the specific rotation recovers to the original value. For more detailed discussion, see the Supporting Information.
40. Yashima, E.; Maeda, K.; Okamoto, Y. Nature 1999, 399, 449-451.
41. Poly-1 also exhibited an optical rotation due to the main chain helical chirality in the presence of other optically active amines, such as (R)-1-(1-naphthyl)ethylamine and (R)-1-cyclohexylethylamine, although the net rotations were rather small compared with those of the poly-1-(R)-2 system.
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