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- Title
Determination of Controlled Self-Assembly of a Paracrystalline Material by Homology Modelling with Hybrid NMR and TEM.
- Authors
Thomas, Brijith; Rombouts, Jeroen; Gupta, Karthick Babu Sai Sankar; Orru, Romano V. A.; Lammertsma, Koop; de Groot, Huub J. M.
- 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.
- Subjects
MOLECULAR self-assembly; HOMOLOGY (Biochemistry); NUCLEAR magnetic resonance spectroscopy; TRANSMISSION electron microscopy; PHOTOSYNTHESIS; SUBSTITUENTS (Chemistry)
- Publication
Chemistry - A European Journal, 2017, Vol 23, Issue 39, p9346
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201701172