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*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


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
Issue number39
Publication statusPublished - 12 Jul 2017


This work is part of the research program of the NWO uNMR distributed large scale facility and was supported by the Biosolar cells project of the Dutch Ministry of Economic Affairs, Agriculture and Innovation. The microscopy was performed in the NECEN cryo-EM facility in Leiden.

FundersFunder number
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerie van Economische Zaken, Landbouw en Innovatie


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


    Dive into the research topics of 'Determination of Controlled Self-Assembly of a Paracrystalline Material by Homology Modelling with Hybrid NMR and TEM'. Together they form a unique fingerprint.

    Cite this