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35048875598
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Although dipyrrin-ZnII complex in which two dipyrrin moieties are almost perpendicular is known to exhibit no chirality, we define configurations Λ and Δ by the moieties including dipyrrin and the neighboring meso-aryl moiety, which is tilted at ca. 45° to the dipyrrin plane, as shown below
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II complex in which two dipyrrin moieties are almost perpendicular is known to exhibit no chirality, we define configurations Λ and Δ by the moieties including dipyrrin and the neighboring meso-aryl moiety, which is tilted at ca. 45° to the dipyrrin plane, as shown below.
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38
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35048829634
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Gaussian 03, Revision C.01, M.J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, O. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Ch
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Gaussian 03, Revision C.01, M.J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, O. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.
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39
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35048815862
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2 overlaps with the major single peak of the achiral isomer, as suggested from the UV/Vis absorption spectra (which differ in two stereoisomers), during the analysis. See Supporting Information.
-
2 overlaps with the major single peak of the achiral isomer, as suggested from the UV/Vis absorption spectra (which differ in two stereoisomers), during the analysis. See Supporting Information.
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-
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40
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35048824221
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The equilibrium constants K between the chiral and meso isomers of C16H33-substituted 1c 2·Zn2 at 60, 20, and, 20°C are 5.4, 4.6, and 4.4, respectively, with the corresponding ΔG° of -4.1, 3.7, and -3.6 kj mol-1. By using van 't Hoff plots, the thermodynamic parameters (ΔH° and ΔS°) of 1c2·Zn2 are estimated to be 1.7 kJ mol-1 and 19 J K-1 mol -1, which are similar to those of 1a2· Zn2 and 1b2·Zn2. The derivative with long alkyl substituents at the dipyrrin units also seems to enable the interconversion between the two stereoisomers, possibly due to the flexible aliphatic chains
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2. The derivative with long alkyl substituents at the dipyrrin units also seems to enable the interconversion between the two stereoisomers, possibly due to the flexible aliphatic chains.
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Under the irradiation of one of the internal β-CH protons of the minor isomer for 60 s and using the hypothetical equation d(M Ai+MAe)/Dt, kA(MAi+MAe, kB(M Bi+MBe, M0Ai-M Ae/T1Ai, M0Ae-M Ae/T1Ae (MAi: the magnetization of the internal β-CH protons of the major isomer (A, M Ae: the magnetization of the external β-CH protons of the major isomer; MBi: the magnetization of the internal β-CH protons of the minor isomer B, MBe: the magnetization of the external β-CH protons of the minor isomer; M0Ai: the magnetization of the internal β-CH protons of the major isomer at thermal equilibrium state, M
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2), respectively.
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