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Volumn 111, Issue 50, 2007, Pages 18605-18614

Thermodynamics and kinetics of formation of orientationally isomeric [2]pseudorotaxanes between α-cyclodextrin and aliphatic chain-linked aromatic donor-viologen acceptor compounds

Author keywords

[No Author keywords available]

Indexed keywords

CYCLODEXTRINS; ETHYLENE; FLUORESCENCE SPECTROSCOPY; NUCLEAR MAGNETIC RESONANCE; PARAFFINS; THERMODYNAMICS;

EID: 38149034264     PISSN: 19327447     EISSN: 19327455     Source Type: Journal    
DOI: 10.1021/jp076314r     Document Type: Article
Times cited : (23)

References (68)
  • 1
    • 0003542983 scopus 로고    scopus 로고
    • Sauvage, J.-P, Dietrich-Buchecker, C, Eds, Wiley-VCH: Weinheim, Germany
    • (a) Sauvage, J.-P.; Dietrich-Buchecker, C., Eds. Molecular Catenanes, Rotaxanes, and Knots; Wiley-VCH: Weinheim, Germany, 1999.
    • (1999) Molecular Catenanes, Rotaxanes, and Knots
  • 5
    • 0008522325 scopus 로고    scopus 로고
    • Reviews on CD-based rotaxanes and pseudorotaxanes, (a) Nepogodiev, S. A.; Stoddart, J. F. Chem. Rev. 1998, 98, 1959.
    • Reviews on CD-based rotaxanes and pseudorotaxanes, (a) Nepogodiev, S. A.; Stoddart, J. F. Chem. Rev. 1998, 98, 1959.
  • 60
    • 38149089075 scopus 로고    scopus 로고
    • 2: C, 61.08; H, 5.64; N, 7.12. Found: C, 60.87; H, 5.75; N, 7.09.
    • 2: C, 61.08; H, 5.64; N, 7.12. Found: C, 60.87; H, 5.75; N, 7.09.
  • 61
    • 38149076777 scopus 로고    scopus 로고
    • in values in Table 1, the fraction of dimer is estimated to be less than 1.2 % in our experimental conditions for fluorescence measurements.
    • in values in Table 1, the fraction of dimer is estimated to be less than 1.2 % in our experimental conditions for fluorescence measurements.
  • 62
    • 34547308105 scopus 로고    scopus 로고
    • Methods for Studies of Cyclodextrin Inclusion Complexation and Excitation Transfer in Cyclodextrin Complexes
    • Douhal A, Ed, Elsevier: Amsterdam, Netherlands
    • Park, J. W. Methods for Studies of Cyclodextrin Inclusion Complexation and Excitation Transfer in Cyclodextrin Complexes. In Cyclodextrin Materials Photochemistry, Photophysics, and Photobiology; Douhal A., Ed.; Elsevier: Amsterdam, Netherlands 2006; pp 1-26.
    • (2006) Cyclodextrin Materials Photochemistry, Photophysics, and Photobiology , pp. 1-26
    • Park, J.W.1
  • 64
    • 38149005141 scopus 로고    scopus 로고
    • 2,obs values with large uncertainty.
    • 2,obs values with large uncertainty.
  • 66
    • 38149086377 scopus 로고    scopus 로고
    • Eq 16 was derived under the assumption of complete dethreading of the [2]pseudorotaxane isomers. When [T]o ≪ [α-CD] o ≪ [OcNH3+]o, the equilibrium concentration of α-CD, α-CD]eq, is approximated as [α-CD]o/([OcNH3+]o· KS, where KS is the binding constant of OcNH3+ with α-CD. As KS, 2400 M-1,34 [α-CD]eq in the presence of 0.1 M OcNH3+ are 1.8 × 10-5 M when [α-CD]o, 4.3 mM and 3.8 × 10-6 M when [α-CD]o, 0.9 mM. The rethreading reaction rate could contribute to the observed dethreading rate constants. The pseudo-first order rethreading rate constants, k(rethreading, k1f,app, k 2f,app)·[α
    • 2r, of 1/α-CD of which uncertainty is comparable to k(rethreading). This supports the reliability of the present method for the determination of dethreading rate constants.
  • 67
    • 38149079155 scopus 로고    scopus 로고
    • The fractions of a thread molecule remaining as P1 and P II [2]pseudorotaxane isomers at equilibrium (fI and fII) are given by fI, K 1,app [α-CD]eq/(1, Kapp[α- CD]eq) and fII, KII,app [α-CD]eq/ 1+Kapp[α-CD]eq, By using the calculated [α-CD]eq values35 in the presence of 0.1 M OcNH3+ and the equilibrium constant data in Table 2, the fI and fII values of 1/α-CD [2]pseudorotaxanes are estimated as 0.007 and 0.10, respectively, when [α-CD]o, 0.9 mM, and 0.024 and 0.34, respectively, when [α-CD]o, 4.3 mM. Similarly, the fI and fII values for 2/α-CD are estimated as 0.0016 and 0.021
    • +. This is a reason why a longer threading time is used for 1 before initiation of the dethreading reaction.


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