Résumé
The self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1′-binaphthyl-2,2′-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)-pyridine termini are reported. Systematic spectroscopic (UV-vis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl<inf>3</inf>, CHCl<inf>3</inf>/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature. (Chemical Equation Presented).
| langue originale | Anglais |
|---|---|
| Pages (de - à) | 8150-8160 |
| Nombre de pages | 11 |
| journal | Journal of the American Chemical Society |
| Volume | 137 |
| Numéro de publication | 25 |
| Les DOIs | |
| état | Publié - 1 juil. 2015 |
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Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers. / Dordević, Luka; Marangoni, Tomas; Miletić, Tanja; Rubio-Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, Davide.
Dans: Journal of the American Chemical Society, Vol 137, Numéro 25, 01.07.2015, p. 8150-8160.Résultats de recherche: Contribution à un journal/une revue › Article
TY - JOUR
T1 - Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers
AU - Dordević, Luka
AU - Marangoni, Tomas
AU - Miletić, Tanja
AU - Rubio-Magnieto, Jenifer
AU - Mohanraj, John
AU - Amenitsch, Heinz
AU - Pasini, Dario
AU - Liaros, Nikos
AU - Couris, Stelios
AU - Armaroli, Nicola
AU - Surin, Mathieu
AU - Bonifazi, Davide
PY - 2015/7/1
Y1 - 2015/7/1
N2 - The self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1′-binaphthyl-2,2′-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)-pyridine termini are reported. Systematic spectroscopic (UV-vis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature. (Chemical Equation Presented).
AB - The self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1′-binaphthyl-2,2′-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)-pyridine termini are reported. Systematic spectroscopic (UV-vis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature. (Chemical Equation Presented).
UR - http://www.scopus.com/inward/record.url?scp=84934782868&partnerID=8YFLogxK
U2 - 10.1021/jacs.5b02448
DO - 10.1021/jacs.5b02448
M3 - Article
AN - SCOPUS:84934782868
VL - 137
SP - 8150
EP - 8160
JO - J. Am. Chem. Soc.
JF - J. Am. Chem. Soc.
SN - 0002-7863
IS - 25
ER -