Determination of Controlled Self-Assembly of a Paracrystalline Material by Homology Modelling with Hybrid NMR and TEM

Brijith Thomas, Jeroen Rombouts, Karthick Babu Sai Sankar Gupta, Romano V.A. Orru, Koop Lammertsma, Huub J.M. de Groot

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Controlling complexity, flexibility, and functionality of synthetic and biomimetic materials requires insight into how molecular functionalities can be exploited for steering their packing. A fused NDI-salphen (NDI=naphthalene diimide) prototypic artificial photosynthesis material, DATZnS, is shown to be comprised of a phenazine motif, in which the alignment of electric dipole moments in a P2/c supramolecular scaffold can be modulated with bulky substituents. They can also be switched between parallel stacks of dipoles running antiparallel in the DATZnS-H compared with parallel stacks of dipoles in polar layers running in opposite directions in the DATZnS(3′-NMe) parent compound. Spatial correlations obtained from HETCOR spectra, collected with a long cross polarization contact time of 2 ms, reveal an antiparallel stacking for the DATZnS-H homologue. These constraints and limited data from TEM are used to construct a structural model within the P2/c space group determined by the molecular C2 symmetry. By using homology modelling, a pseudo octahedral coordination of the Zn is shown to follow the packing-induced chirality with enantiomeric pairs of the Λ and Δ forms alternating along antiparallel stacks. The model helps to understand how the steric hindrance modulates the self-assembly in this novel class of fused materials by steric hindrance at the molecular level.

Original languageEnglish
Pages (from-to)9346-9351
Number of pages6
JournalChemistry - A European Journal
Volume23
Issue number39
DOIs
Publication statusPublished - 12 Jul 2017

Fingerprint

Self assembly
Biomimetic materials
Nuclear magnetic resonance
Electric dipole moments
Transmission electron microscopy
Photosynthesis
Chirality
Naphthalene
Scaffolds
Polarization
salphen
Direction compound
naphthalenediimide
phenazine

Keywords

  • mas nmr
  • phenazine
  • self-assembly
  • supra-molecular chemistry
  • tem

Cite this

Thomas, Brijith ; Rombouts, Jeroen ; Gupta, Karthick Babu Sai Sankar ; Orru, Romano V.A. ; Lammertsma, Koop ; de Groot, Huub J.M. / Determination of Controlled Self-Assembly of a Paracrystalline Material by Homology Modelling with Hybrid NMR and TEM. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 39. pp. 9346-9351.
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Determination of Controlled Self-Assembly of a Paracrystalline Material by Homology Modelling with Hybrid NMR and TEM. / Thomas, Brijith; Rombouts, Jeroen; Gupta, Karthick Babu Sai Sankar; Orru, Romano V.A.; Lammertsma, Koop; de Groot, Huub J.M.

In: Chemistry - A European Journal, Vol. 23, No. 39, 12.07.2017, p. 9346-9351.

Research output: Contribution to JournalArticleAcademicpeer-review

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