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Photochromic spirooxazines functionalized with oligomers: investigation of core−oligomer interactions and photomerocyanine isomer interconversion using NMR spectroscopy and DFT

Lachlan H. Yee, Southern Cross University
Tracey L. Hanley, Bragg Institute, ANSTO
Richard A. Evans, CSIRO Molecular and Health Technologies
Thomas P. Davis, University of New South Wales
Graham E. Ball, University of New South Wales

Abstract

Photochromic spirooxazines functionalized with poly(ethylene glycol) (PEG) and poly(dimethylsiloxane) (PDMS) oligomers were monitored using NMR spectroscopy at temperatures between 193 and 233 K before and after in situ exposure to UV irradiation. NOESY and ROESY experiments reveal the TTC (trans−s-trans−cis) isomer to be the dominant merocyanine isomer formed on photolysis, with some CTC (cis−s-trans−cis) isomer also present. Significant ROE cross peaks were observed between the “bulk” of the oligomeric units and protons across the entire photochromic core of the molecule, the intensity of these cross peaks suggesting that the interaction of the oligomer side chain and core of the molecule is significantly enhanced by the permanent attachment, especially with the PDMS side chain. The 2D NMR spectra indicate that there is exchange between the TTC and CTC isomers even at 193 K. This isomerization of the parent spirooxazine compounds, lacking the oligomeric side chains, was found to be acid-catalyzed, and DFT calculations support the strong possibility that it is the protonated merocyanine form that undergoes the facile isomerization process. Interconversion of the different merocyanine isomers is suggested to be fast on the NMR time scale under many experimental conditions, precluding the observation of different isomers using NMR spectroscopy at room temperature.

Suggested Citation

Yee, LH, Hanley, TL, Evans. RA, Davis, TP & Ball, GE 2010, 'Photochromic spirooxazines functionalized with oligomers: investigation of core−oligomer interactions and photomerocyanine isomer interconversion using NMR spectroscopy and DFT', Journal of Organic Chemistry, vol. 75, no. 9, pp. 2851-2860.

Published version available from:

http://dx.doi.org/10.1021/jo100081g