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Theoretical Investigation of Macrodipoles in Supramolecular Columnar Stackings

Title data

Albuquerque, Rodrigo Q. ; Timme, Andreas ; Kress, Roman ; Senker, Jürgen ; Schmidt, Hans-Werner:
Theoretical Investigation of Macrodipoles in Supramolecular Columnar Stackings.
In: Chemistry : a European Journal. Vol. 19 (2013) Issue 5 . - pp. 1647-1657.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.201202507

Official URL: Volltext

Abstract in another language

Supramolecular columnar assemblies are known to form intrinsic macrodipoles, which play an important role in intercolumnar interactions and govern the self-assembly on the mesoscale. A prominent class that provides this feature are trisamide derivatives, namely, 1,3,5-benzenetrisamides and 1,3,5-cyclohexanetrisamides. The understanding of how subtle changes in the chemical structure influence the columnar order and consequently the macrodipole formation is of fundamental interest. Here we report on the theoretical investigation of trisamide derivatives and how the formed macrodipole is related to the properties of the columnar aggregates. Calculations were carried out on a semiempirical level using the PM6 approximation, which is able to treat weak interactions like hydrogen bonding and dispersion forces with a sufficient accuracy. We have compared the influence of a benzene core with a cyclohexane core on the macrodipole formation. It was revealed that columnar aggregates based on 1,3,5-cyclohexanetrisamides have much higher dipole moments than those formed with aromatic cores. A cooperative effect was found during aggregation, as longer aggregates show stronger hydrogen bonding, thereby facilitating the addition of the next molecule. We have also investigated the influence of the amide connection on the strength of the formed macrodipole. The trends observed for the macrodipole strength correlate with the cal-cu-lated heat of formation. If the amide groups are inverted, the strength of the macrodipole is reduced and the negative heat of formation is increased. HOMO-LUMO gaps were correlated with the inverse of the dipole moment per monomer unit, thus indicating that the macrodipole might act as a perturbation to the supramolecular assemblies.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry III
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry III > Chair Anorganic Chemistry III - Univ.-Prof. Dr. Jürgen Senker
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Macromolecular Chemistry I
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Macromolecular Chemistry I > Chair Macromolecular Chemistry I - Univ.-Prof. Dr. Hans-Werner Schmidt
Profile Fields
Profile Fields > Advanced Fields
Profile Fields > Advanced Fields > Polymer and Colloid Science
Profile Fields > Advanced Fields > Advanced Materials
Research Institutions
Research Institutions > Research Centres
Research Institutions > Research Centres > Bayreuth Institute of Macromolecular Research - BIMF
Research Institutions > Research Centres > Bayreuth Center for Colloids and Interfaces - BZKG
Research Institutions > Collaborative Research Centers, Research Unit
Research Institutions > Collaborative Research Centers, Research Unit > SFB 840 Von partikulären Nanosystemen zur Mesotechnologie
Research Institutions > Collaborative Research Centers, Research Unit > SFB 840 Von partikulären Nanosystemen zur Mesotechnologie > SFB 840 - TP B 4
Graduate Schools
Graduate Schools > Bayreuth Graduate School of Mathematical and Natural Sciences (BayNAT)
Graduate Schools > Bayreuth Graduate School of Mathematical and Natural Sciences (BayNAT) > Photophysics of Synthetic and Biological Multichromophoric Systems
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 01 Dec 2014 09:56
Last Modified: 06 Jul 2015 07:41
URI: https://eref.uni-bayreuth.de/id/eprint/4266