Proton exchange and isomerisation reactions of photochromic and reverse photochromic spiro-pyrans and their merocyanine forms

Jonathan Hobley, Vincenzo Malatesta, Roberto Millini, Luciano Montanari, Wallace O Neil Parker

Research output: Contribution to journalArticlepeer-review

95 Citations (Scopus)

Abstract

Photochromic 1',3',3'-trimethyl-6,8-dinitro-spiro- [2H-1-benzopyran- 2,2-indoline], (6,8-dinitro BIPS) has been studied in different solvents using 1H-NMR techniques, UV/visible spectroscopy, X-ray diffraction and electrospray ionisation mass spectroscopy (ESI-MS). Molar decadic absorption coefficients for 6,8-dinitro BIPS were found to range between 35 000-45 000 dm3 mol-1 cm-1. 1H-1H NOESY and 1H-NMR experiments have established that in solution the merocyanine form of 6,8-dinitro BIPS is in rapid exchange between the trans-trans-cis (TTC) and trans-trans-trans (TTT) isomers. The 3B proton on the central bridging double bond of spiro-pyran merocyanines is labile in organic solvents. The closed form of 6,8-dinitro BIPS enantiomerises about the spiro C(2) carbon at a rate of 18 s-1 at 300 K. The activation energy for this process was estimated to be 46 kJ mol-1 using dynamic NMR.

Original languageEnglish
Pages (from-to)3259-3267
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume1
Issue number14
DOIs
Publication statusPublished - 1999 Jul 15

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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