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A Remarkably Complex Supramolecular Hydrogen-Bonded Decameric Capsule Formed from an Enantiopure C2-Symmetric Monomer by Solvent-Responsive Aggregation.

Račkauskaitė, Dovilė; Bergquist, Karl-Erik LU ; Shi, Qixun LU ; Sundin, Anders LU ; Butkus, Eugenijus; Wärnmark, Kenneth LU and Orentas, Edvinas (2015) In Journal of the American Chemical Society 137(33). p.10536-10546
Abstract
The formation of an unprecedented decameric capsule in carbon disulfide, held together by the combination of double and triple hydrogen bonds between isocytosine units embedded in an enantiomerically pure bicyclic framework is reported. The aggregation occurs via symmetry breaking of the enantiopure intrinsically C2-symmetric monomer brought about by solvent, induced tautomerization of the hydrogen-bonding unit. We show that the topology of the aggregate is responsive to the solvent in which the assembly takes place. In this study we demonstrate that in carbon disulfide the chiral decameric cavity aggregate consisting of three forms of the same monomer, differing in their hydrogen bonding to each other is selectively formed, representing a... (More)
The formation of an unprecedented decameric capsule in carbon disulfide, held together by the combination of double and triple hydrogen bonds between isocytosine units embedded in an enantiomerically pure bicyclic framework is reported. The aggregation occurs via symmetry breaking of the enantiopure intrinsically C2-symmetric monomer brought about by solvent, induced tautomerization of the hydrogen-bonding unit. We show that the topology of the aggregate is responsive to the solvent in which the assembly takes place. In this study we demonstrate that in carbon disulfide the chiral decameric cavity aggregate consisting of three forms of the same monomer, differing in their hydrogen bonding to each other is selectively formed, representing a tube-like structure capped with two C2-symmetric monomers. The large cylindrical cavity produced selectively accommodates one partially solvated C60 molecule, and molecular dynamic simulations revealed the special role of the solvent in the inclusion mechanism. The strategy described herein represents the first step toward the creation of a new class of hydrogen-bonded tubular objects from only one small symmetric building block by solvent-responsive aggregation. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
137
issue
33
pages
10536 - 10546
publisher
The American Chemical Society
external identifiers
  • pmid:25950402
  • wos:000360321100024
  • scopus:84941671323
ISSN
1520-5126
DOI
10.1021/jacs.5b03160
language
English
LU publication?
yes
id
ea0b02d2-6c3e-4b4c-ab0f-555846f273bc (old id 5456742)
date added to LUP
2015-06-23 17:13:10
date last changed
2017-11-05 03:01:29
@article{ea0b02d2-6c3e-4b4c-ab0f-555846f273bc,
  abstract     = {The formation of an unprecedented decameric capsule in carbon disulfide, held together by the combination of double and triple hydrogen bonds between isocytosine units embedded in an enantiomerically pure bicyclic framework is reported. The aggregation occurs via symmetry breaking of the enantiopure intrinsically C2-symmetric monomer brought about by solvent, induced tautomerization of the hydrogen-bonding unit. We show that the topology of the aggregate is responsive to the solvent in which the assembly takes place. In this study we demonstrate that in carbon disulfide the chiral decameric cavity aggregate consisting of three forms of the same monomer, differing in their hydrogen bonding to each other is selectively formed, representing a tube-like structure capped with two C2-symmetric monomers. The large cylindrical cavity produced selectively accommodates one partially solvated C60 molecule, and molecular dynamic simulations revealed the special role of the solvent in the inclusion mechanism. The strategy described herein represents the first step toward the creation of a new class of hydrogen-bonded tubular objects from only one small symmetric building block by solvent-responsive aggregation.},
  author       = {Račkauskaitė, Dovilė and Bergquist, Karl-Erik and Shi, Qixun and Sundin, Anders and Butkus, Eugenijus and Wärnmark, Kenneth and Orentas, Edvinas},
  issn         = {1520-5126},
  language     = {eng},
  number       = {33},
  pages        = {10536--10546},
  publisher    = {The American Chemical Society},
  series       = {Journal of the American Chemical Society},
  title        = {A Remarkably Complex Supramolecular Hydrogen-Bonded Decameric Capsule Formed from an Enantiopure C2-Symmetric Monomer by Solvent-Responsive Aggregation.},
  url          = {http://dx.doi.org/10.1021/jacs.5b03160},
  volume       = {137},
  year         = {2015},
}