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Determination of Controlled Self‐Assembly of a Paracrystalline Material by Homology Modelling with Hybrid NMR and TEM
Author(s) -
Thomas Brijith,
Rombouts Jeroen,
Gupta Karthick Babu Sai Sankar,
Orru Romano V. A.,
Lammertsma Koop,
de Groot Huub J. M.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701172
Subject(s) - antiparallel (mathematics) , crystallography , steric effects , supramolecular chemistry , stacking , dipole , chemistry , stereochemistry , self assembly , materials science , molecular dynamics , computational chemistry , nanotechnology , crystal structure , physics , organic chemistry , quantum mechanics , magnetic field
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 P 2/ 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 P 2/ c space group determined by the molecular C 2 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.