A Hybrid Solid-State NMR and Electron Microscopy Structure-Determination Protocol for Engineering Advanced para-Crystalline Optical Materials

Brijith Thomas, Jeroen Rombouts, Gert T. Oostergetel, Karthick B.S.S. Gupta, Francesco Buda, Koop Lammertsma, Romano Orru, Huub J.M. de Groot

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Hybrid magic-angle spinning (MAS) NMR spectroscopy and TEM were demonstrated for de novo structure determination of para-crystalline materials with a bioinspired fused naphthalene diimide (NDI)–salphen–phenazine prototype light-harvesting compound. Starting from chiral building blocks with C2 molecular symmetry, the asymmetric unit was determined by MAS NMR spectroscopy, index low-resolution TEM diffraction data, and resolve reflection conditions, and for the first time the ability to determine the space group from reciprocal space data using this hybrid approach was shown. Transfer of molecular C2 symmetry into P2/c packing symmetry provided a connection across length scales to overcome both lack of long-range order and missing diffraction-phase information. Refinement with heteronuclear distance constraints confirmed the racemic P2/c packing that was scaffolded by molecular recognition of salphen zinc in a pseudo-octahedral environment with bromide and with alkyl chains folding along the phenazine. The NDI light-harvesting stacks ran orthogonal to the intermolecular electric dipole moment present in the solid. Finally, the orientation of flexible lamellae on an electrode surface was determined.

Original languageEnglish
Pages (from-to)3280-3284
Number of pages5
JournalChemistry - A European Journal
Volume23
Issue number14
DOIs
Publication statusPublished - 8 Mar 2017

Fingerprint

Magic angle spinning
Optical materials
Naphthalene
Electron microscopy
Nuclear magnetic resonance spectroscopy
Diffraction
Nuclear magnetic resonance
Electric dipole moments
Crystalline materials
Transmission electron microscopy
Molecular recognition
Bromides
Zinc
Electrodes
naphthalenediimide
phenazine
salphen

Keywords

  • electron microscopy
  • magic-angle spinning
  • NMR spectroscopy
  • photochemistry
  • self-assembly

Cite this

Thomas, Brijith ; Rombouts, Jeroen ; Oostergetel, Gert T. ; Gupta, Karthick B.S.S. ; Buda, Francesco ; Lammertsma, Koop ; Orru, Romano ; de Groot, Huub J.M. / A Hybrid Solid-State NMR and Electron Microscopy Structure-Determination Protocol for Engineering Advanced para-Crystalline Optical Materials. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 14. pp. 3280-3284.
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A Hybrid Solid-State NMR and Electron Microscopy Structure-Determination Protocol for Engineering Advanced para-Crystalline Optical Materials. / Thomas, Brijith; Rombouts, Jeroen; Oostergetel, Gert T.; Gupta, Karthick B.S.S.; Buda, Francesco; Lammertsma, Koop; Orru, Romano; de Groot, Huub J.M.

In: Chemistry - A European Journal, Vol. 23, No. 14, 08.03.2017, p. 3280-3284.

Research output: Contribution to JournalArticleAcademicpeer-review

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