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Journal of the American Chemical Society
Volumn 131, Issue 30, 2009, Pages 10719-10732
Mechanism of helix induction in poly(4-carboxyphenyl isocyanide) with chiral amines and memory of the macromolecular helicity and its helical structures
Author keywords

[No Author keywords available]
Indexed keywords

AQUEOUS-ORGANIC SOLUTIONS; CHAIN STIFFNESS; CHIRAL AMINES; CIRCULAR DICHROISM; DENSITY FUNCTIONAL THEORY CALCULATIONS; DOUBLE BONDS; HELICAL STRUCTURES; HELICITY INDUCTION; INDUCED CIRCULAR DICHROISM; INDUCTION MECHANISM; ISOCYANIDE; LIQUID CRYSTALLINE POLYMER; MACROMOLECULAR HELICITY; METHYL ESTERS; MONOMER UNITS; ONE-HANDED; OPTICAL ACTIVITY; OPTICALLY ACTIVE; PERSISTENCE LENGTH; PHENYL ISOCYANIDE; POLYMER BACKBONES; REPEATING UNIT; SPECTROSCOPIC MEASUREMENTS; STRUCTURAL CHANGE; STRUCTURAL INFORMATION; THEORETICAL CALCULATIONS; UNIAXIALLY ORIENTED FILMS; WATER MIXTURE; XRD; XRD ANALYSIS; XRD MEASUREMENTS;
EID: 68049110616     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja904128d     Document Type: Article
Times cited : (99)
References (132)
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    • For other leading references on helical polyisocyanides prepared by the polymerization of the corresponding optically active monomers, see: (l) Cornelissen, J. J. L. M, Fischer, M, Sommerdijk, N. A. J. M, Nolte, R. J. M. Science 1998, 280, 1427-1430
    • For other leading references on helical polyisocyanides prepared by the polymerization of the corresponding optically active monomers, see: (l) Cornelissen, J. J. L. M.; Fischer, M.; Sommerdijk, N. A. J. M.; Nolte, R. J. M. Science 1998, 280, 1427-1430.
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    • Molecular orbital calculations of poly(iminomethylene) using semi-empirical methods were also conducted
    • (a) Clericuzio, M.; Alagona, G.; Ghio, C.; Salvadori, P. J. Am. Chem. Soc. 1997, 119, 1059-1071. Molecular orbital calculations of poly(iminomethylene) using semi-empirical methods were also conducted.
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    • Clericuzio, M.1    Alagona, G.2    Ghio, C.3    Salvadori, P.4
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    • Recently, we have reported the helix-sense-selective living polymerization of an optically active phenyl isocyanide bearing an L-alanine pendant with a long decyl chain with the achiral μ-ethynediyl Pt-Pd catalyst that unprecedentedly produced both right- and left-handed helical, rigid-rod polyisocyanides at once with a different molecular weight and a narrow molecular weight distribution, which could be separated into each helix in a facile fractionation with acetone. The structures of both right- and left-handed helical polyisocyanides were proposed to be a 15-unit/4-turn (15/4) helix on the basis of X-ray analyses of the corresponding oriented films.10h However, the detailed structural analysis, including a possible configurational and conformational isomerism of the main-chain, has never been pursued
    • 10h However, the detailed structural analysis, including a possible configurational and conformational isomerism of the main-chain, has never been pursued.
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    • For chiral memory effect of other macromolecular and supramolecular systems, see: l
    • For chiral memory effect of other macromolecular and supramolecular systems, see: (l) Furusho, Y.; Kimura, T.; Mizuno, Y.; Aida, T. J. Am. Chem. Soc. 1997, 119, 5267-5268.
    • (1997) J. Am. Chem. Soc , vol.119 , pp. 5267-5268
    • Furusho, Y.1    Kimura, T.2    Mizuno, Y.3    Aida, T.4
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    • 2O remains obscure, but this method may be useful to obtain high-molecular-weight polyisocyanides.
    • 2O remains obscure, but this method may be useful to obtain high-molecular-weight polyisocyanides.
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    • 13C were also observed (see Figure S6, Supporting Information).
    • 13C were also observed (see Figure S6, Supporting Information).
  • 97
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    • A similar dynamic helical model has also been proposed by Cornelissen, Nolte, and co-workers for helical poly(isocyanopeptide)s derived from β-amino acids. See ref 10e
    • A similar dynamic helical model has also been proposed by Cornelissen, Nolte, and co-workers for helical poly(isocyanopeptide)s derived from β-amino acids. See ref 10e.
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    • The persistence length (q) is a useful measure to evaluate the stiffness of rodlike polymers, but only a limited number of q values have been determined for synthetic helical polymers. See: (a) Sato, T.; Teramoto, A. Adv. Polym. Sci. 1996, 126, 85-161.
    • The persistence length (q) is a useful measure to evaluate the stiffness of rodlike polymers, but only a limited number of q values have been determined for synthetic helical polymers. See: (a) Sato, T.; Teramoto, A. Adv. Polym. Sci. 1996, 126, 85-161.
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    • Persistence length values of certain polyisocyanide derivatives have been measured
    • (h) Okoshi, K.; Sakurai, S.-i.; Ohsawa, S.; Kumaki, J.; Yashima, E. Angew. Chem., Int. Ed. 2006, 45, 8173-8176. Persistence length values of certain polyisocyanide derivatives have been measured.
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    • The densities of the HMW-poly-1-Me, HMW-poly-1a-Me, and HMW-h-poly-1b-Me films were measured by the standard flotation method in a KBr saturated aqueous solution - water mixture at ambient temperature (20-25°C).
    • The densities of the HMW-poly-1-Me, HMW-poly-1a-Me, and HMW-h-poly-1b-Me films were measured by the standard flotation method in a KBr saturated aqueous solution - water mixture at ambient temperature (20-25°C).
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    • The MM calculations of the s-cis-isotactic 18/5 helical structure of poly-1a-Me and poly-1′-Me with a repeating structure unit (1-mer) for the periodicity like h-poly-1b-Me revealed that the energy-minimized conformation had a much higher energy than the 10/3 helical h-poly-1b-Me. We then considered a plausible helical structure of poly-1a-Me and poly-1′-Me that has a repeating structure unit (2-mer) for the periodicity (Chart S3, Supporting Information) and found that the energy-minimized 9/5 helical structure with an alternating s-cis and s-trans conformation had a much lower energy than h-poly-1b-Me (see the Supporting Information).
    • The MM calculations of the s-cis-isotactic 18/5 helical structure of poly-1a-Me and poly-1′-Me with a repeating structure unit (1-mer) for the periodicity like h-poly-1b-Me revealed that the energy-minimized conformation had a much higher energy than the 10/3 helical h-poly-1b-Me. We then considered a plausible helical structure of poly-1a-Me and poly-1′-Me that has a repeating structure unit (2-mer) for the periodicity (Chart S3, Supporting Information) and found that the energy-minimized 9/5 helical structure with an alternating s-cis and s-trans conformation had a much lower energy than h-poly-1b-Me (see the Supporting Information).
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    • Although the IR and NMR spectral results suggest that the mainchain configuration of poly-1a-Me may differ from that of h-poly- 1b-Me Figures 3 and S6, the optimized helical structure of poly-1a-Me obtained by the empirical MM calculations appears to be isotactic; a syndiotactic structure may likely be more plausible for poly-1a-Me to explain the differences in their IR and NMR spectra. Apparently, more detailed nonempirical calculations are required to determine the main-chain configuration of poly-1a-Me
    • Although the IR and NMR spectral results suggest that the mainchain configuration of poly-1a-Me may differ from that of h-poly- 1b-Me (Figures 3 and S6), the optimized helical structure of poly-1a-Me obtained by the empirical MM calculations appears to be isotactic; a syndiotactic structure may likely be more plausible for poly-1a-Me to explain the differences in their IR and NMR spectra. Apparently, more detailed nonempirical calculations are required to determine the main-chain configuration of poly-1a-Me.
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    • The optimized s-trans isotactic PPI has a 5/2 helix with two monomer unitsas a repeatingunit for the periodicity (see Figure S2 and the SupportingInformation). The result also proves the validity of the assigned s-cis isotactic helical structure of h-poly-1b-Me.
    • The optimized s-trans isotactic PPI has a 5/2 helix with two monomer unitsas a repeatingunit for the periodicity (see Figure S2 and the SupportingInformation). The result also proves the validity of the assigned s-cis isotactic helical structure of h-poly-1b-Me.
  • 129
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    • Because PPI and h-poly-1b-Me possess different pendant groups, the calculated IR and VCD of PPI in other vibration regions were not in agreement with the observed IR and VCD spectra of h-poly-1b-Me.
    • Because PPI and h-poly-1b-Me possess different pendant groups, the calculated IR and VCD of PPI in other vibration regions were not in agreement with the observed IR and VCD spectra of h-poly-1b-Me.
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    • Takei, F, Hayashi, H, Onitsuka, K, Kobayashi, N, Takahashi, S. Angew. Chem, Int. Ed. 2001, 40, 4092-4094. The helical sense of a one-handed helical polyguanidine is also assigned on the basis of its observed and calculated VCD spectra; see ref 3b
    • (a) Takei, F.; Hayashi, H.; Onitsuka, K.; Kobayashi, N.; Takahashi, S. Angew. Chem., Int. Ed. 2001, 40, 4092-4094. The helical sense of a one-handed helical polyguanidine is also assigned on the basis of its observed and calculated VCD spectra; see ref 3b.
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    • For other examples of helical sense assignments of polyisocyanides, see ref 7 and the following: (b) Cornelissen, J. J. L. M, Sommerdijk, N. A. J. M, Nolte, R. J. M. Macromol. Chem. Phys. 2002, 203, 1625-1630
    • For other examples of helical sense assignments of polyisocyanides, see ref 7 and the following: (b) Cornelissen, J. J. L. M.; Sommerdijk, N. A. J. M.; Nolte, R. J. M. Macromol. Chem. Phys. 2002, 203, 1625-1630.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.