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Tribenzotriquinacene receptors for C60 fullerene rotors: towards C3 symmetrical chiral stators for unidirectionally operating nanoratchets

(2014) CHEMISTRY-A EUROPEAN JOURNAL. 20(29). p.9100-9110
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Abstract
The synthesis of a stereochemically pure concave tribenzotriquinacene receptor (7) for C-60 fullerene, possessing C-3 point group symmetry, by threefold condensation of C-2-symmetric 1,2-diketone synthons (5) and a hexaaminotribenzotriquinacene core (6) is described. The chiral diketone was synthesized in a five-step reaction sequence starting from C-2h-symmetric 2,6-di-tert-butylanthracene. The highly diastereo-discriminating Diels-Alder reaction of 2,6-di-tertbutylanthracene with fumaric acid di(-)menthyl ester, catalyzed by aluminium chloride, is the relevant stereochemistry introducing step. The structure of the fullerene receptor was verified by H-1 and C-13 NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. VCD and ECD spectra were recorded, which were corroborated by ab initio DFT calculations, establishing the chiral nature of 7 with about 99.7% ee, based on the ee (99.9%) of the chiral synthon (1). The absolute configuration of 7 could thus be established as all-S [(2S,7S,16S,21S,30S,35S)-(7)]. Spectroscopic titration experiments reveal that the host forms 1: 1 complexes with either pure fullerene (C-60) or fullerene derivatives, such as rotor 1'-(4-nitrophenyl)-3'-(4-N,N-dimethylaminophenyl)-pyrazolino[4',5':1,2][60]fullerene (R). The complex stability constants of the complexes dissolved in CHCl3/CS2 (1:1 vol.%) are K([C-60 subset of 7])= 319(+/- 156) M-1 and K([R subset of 7])= 110(+/- 50) M-1. With molecular dynamics simulations using a first-principles parameterized force field the asymmetry of the rotational potential for [R subset of 7] was shown, demonstrating the potential suitability of receptor 7 to act as a stator in a unidirectionally operating nanoratchet.
Keywords
tribenzotriquinacene, self-assembly, VIBRATIONAL CIRCULAR-DICHROISM, MOLECULAR ROTARY MOTOR, DETERMINE ABSOLUTE-CONFIGURATION, X-RAY CRYSTALLOGRAPHY, AB-INITIO CALCULATION, BROWNIAN MOTORS, C-3-SYMMETRICAL TRIBENZOTRIQUINACENE, THEORETICAL DESIGN, BUILDING-BLOCKS, DRIVEN, host-guest systems nanoratchets, fullerenes, molecular devices

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MLA
Bredenkötter, Björn, Maciej Grzywa, Mohammad Alaghemandi, et al. “Tribenzotriquinacene Receptors for C60 Fullerene Rotors: Towards C3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets.” CHEMISTRY-A EUROPEAN JOURNAL 20.29 (2014): 9100–9110. Print.
APA
Bredenkötter, B., Grzywa, M., Alaghemandi, M., Schmid, R., Herrebout, W., Bultinck, P., & Volkmer, D. (2014). Tribenzotriquinacene receptors for C60 fullerene rotors: towards C3 symmetrical chiral stators for unidirectionally operating nanoratchets. CHEMISTRY-A EUROPEAN JOURNAL, 20(29), 9100–9110.
Chicago author-date
Bredenkötter, Björn, Maciej Grzywa, Mohammad Alaghemandi, Rochus Schmid, Wouter Herrebout, Patrick Bultinck, and Dirk Volkmer. 2014. “Tribenzotriquinacene Receptors for C60 Fullerene Rotors: Towards C3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets.” Chemistry-a European Journal 20 (29): 9100–9110.
Chicago author-date (all authors)
Bredenkötter, Björn, Maciej Grzywa, Mohammad Alaghemandi, Rochus Schmid, Wouter Herrebout, Patrick Bultinck, and Dirk Volkmer. 2014. “Tribenzotriquinacene Receptors for C60 Fullerene Rotors: Towards C3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets.” Chemistry-a European Journal 20 (29): 9100–9110.
Vancouver
1.
Bredenkötter B, Grzywa M, Alaghemandi M, Schmid R, Herrebout W, Bultinck P, et al. Tribenzotriquinacene receptors for C60 fullerene rotors: towards C3 symmetrical chiral stators for unidirectionally operating nanoratchets. CHEMISTRY-A EUROPEAN JOURNAL. 2014;20(29):9100–10.
IEEE
[1]
B. Bredenkötter et al., “Tribenzotriquinacene receptors for C60 fullerene rotors: towards C3 symmetrical chiral stators for unidirectionally operating nanoratchets,” CHEMISTRY-A EUROPEAN JOURNAL, vol. 20, no. 29, pp. 9100–9110, 2014.
@article{5700489,
  abstract     = {The synthesis of a stereochemically pure concave tribenzotriquinacene receptor (7) for C-60 fullerene, possessing C-3 point group symmetry, by threefold condensation of C-2-symmetric 1,2-diketone synthons (5) and a hexaaminotribenzotriquinacene core (6) is described. The chiral diketone was synthesized in a five-step reaction sequence starting from C-2h-symmetric 2,6-di-tert-butylanthracene. The highly diastereo-discriminating Diels-Alder reaction of 2,6-di-tertbutylanthracene with fumaric acid di(-)menthyl ester, catalyzed by aluminium chloride, is the relevant stereochemistry introducing step. The structure of the fullerene receptor was verified by H-1 and C-13 NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. VCD and ECD spectra were recorded, which were corroborated by ab initio DFT calculations, establishing the chiral nature of 7 with about 99.7% ee, based on the ee (99.9%) of the chiral synthon (1). The absolute configuration of 7 could thus be established as all-S [(2S,7S,16S,21S,30S,35S)-(7)]. Spectroscopic titration experiments reveal that the host forms 1: 1 complexes with either pure fullerene (C-60) or fullerene derivatives, such as rotor 1'-(4-nitrophenyl)-3'-(4-N,N-dimethylaminophenyl)-pyrazolino[4',5':1,2][60]fullerene (R). The complex stability constants of the complexes dissolved in CHCl3/CS2 (1:1 vol.%) are K([C-60 subset of 7])= 319(+/- 156) M-1 and K([R subset of 7])= 110(+/- 50) M-1. With molecular dynamics simulations using a first-principles parameterized force field the asymmetry of the rotational potential for [R subset of 7] was shown, demonstrating the potential suitability of receptor 7 to act as a stator in a unidirectionally operating nanoratchet.},
  author       = {Bredenkötter, Björn and Grzywa, Maciej and Alaghemandi, Mohammad and Schmid, Rochus and Herrebout, Wouter and Bultinck, Patrick and Volkmer, Dirk},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keywords     = {tribenzotriquinacene,self-assembly,VIBRATIONAL CIRCULAR-DICHROISM,MOLECULAR ROTARY MOTOR,DETERMINE ABSOLUTE-CONFIGURATION,X-RAY CRYSTALLOGRAPHY,AB-INITIO CALCULATION,BROWNIAN MOTORS,C-3-SYMMETRICAL TRIBENZOTRIQUINACENE,THEORETICAL DESIGN,BUILDING-BLOCKS,DRIVEN,host-guest systems nanoratchets,fullerenes,molecular devices},
  language     = {eng},
  number       = {29},
  pages        = {9100--9110},
  title        = {Tribenzotriquinacene receptors for C60 fullerene rotors: towards C3 symmetrical chiral stators for unidirectionally operating nanoratchets},
  url          = {http://dx.doi.org/10.1002/chem.201304980},
  volume       = {20},
  year         = {2014},
}

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