Carbon-13 chemical shift tensors in polycyclic aromatic compounds. 6. Single-crystal study of perylene

Journal Article · Wed May 22 04:00:00 EDT 1996 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja954052d· OSTI ID:264042

Iuliucci, R J; Phung, C G; Facelli, J C; Grant, D M ^[1]

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1. Univ. of Utah, Salt Lake City, UT (United States)

The 40 chemical shift tensors of single-crystal perylene in the {alpha} crystalline form have been determined with a precision of 0.30 ppm using {sub 13}C chemical shift-chemical shift correlation spectroscopy. The in-plane anisotropy of these tensors describes the delocalization of {pi}-electrons at the inner {alpha} position, which is similar to that found in biaryl linkages rather than typical bridgehead carbons. Molecular distortions, originated in intermolecular interactions and associated with chemical shifts of up to 5 ppm in similar carbons of perylene, have been detected indicating that the accuracy in the shift tensors measured in this study is adequate to probe crystalline effects upon the electronic and molecular structure. The systematic tilt observed in the orientation of the smallest principal components, {delta}-33, supports the X-ray observation that the molecules bend about their long axis by 1-2{degree}. Chemical shift calculations, using ab initio methods, are in good agreement with the experimental tensors and provide insight into the observed variation of chemical shifts in terms of molecular geometry. 34 refs., 5 figs., 3 tabs.

• OSTI ID: 264042
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 20 Vol. 118; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
99 GENERAL AND MISCELLANEOUS
AROMATICS
CALCULATION METHODS
CARBON 13
CHEMICAL SHIFT
ELECTRONIC STRUCTURE
MOLECULAR MODELS
MOLECULAR STRUCTURE
NMR SPECTRA
PERYLENE
POLYCYCLIC AROMATIC HYDROCARBONS
TENSORS