Solvent clathrate driven dynamic stereomutation of a supramolecular polymer with molecular pockets

C. Kulkarni, P.A. Korevaar, K.K. Bejagam, A.R.A. Palmans, E.W. Meijer, S.J. George

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Uittreksel

Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3, 5- dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of selfassembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.

Originele taal-2Engels
Pagina's (van-tot)13867-13875
Aantal pagina's9
TijdschriftJournal of the American Chemical Society
Volume139
Nummer van het tijdschrift39
DOI's
StatusGepubliceerd - 2017

Vingerafdruk

Polymers
Thermodynamics
Molecules
Imides
Alkanes
Chirality
Molecular Dynamics Simulation
Molecular Structure
Paraffins
Self assembly
Molecular structure
Molecular dynamics
Substitution reactions
Enzymes
Monomers
Electrons
Kinetics
Temperature
Computer simulation

Citeer dit

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title = "Solvent clathrate driven dynamic stereomutation of a supramolecular polymer with molecular pockets",
abstract = "Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3, 5- dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to {"}molecular pockets{"} in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of selfassembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.",
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Solvent clathrate driven dynamic stereomutation of a supramolecular polymer with molecular pockets. / Kulkarni, C.; Korevaar, P.A.; Bejagam, K.K.; Palmans, A.R.A.; Meijer, E.W.; George, S.J.

In: Journal of the American Chemical Society, Vol. 139, Nr. 39, 2017, blz. 13867-13875.

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

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AU - Meijer, E.W.

AU - George, S.J.

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