Effects of aromatic substitution on the photodimerization kinetics of β-trans cinnamic acid derivatives studied with 13C solid-state NMR

Isa Fonseca, Maria Baias, Sophia E. Hayes, Chris J. Pickard, Marko Bertmer

Research output: Contribution to journalArticle

Abstract

In our efforts to study photodimerizations in the solid state, we present data on the influence of the position of aromatic substitution by bromine on the photodimerization rate in cinnamic acid derivatives. Results were obtained by 13C CPMAS NMR spectroscopy together with chemical shift tensor analysis, DFT calculations using the NMR-CASTEP program, and crystal structure data. Reaction rates are highest for para bromo substitution, whose parent crystal structure was solved in this work. To explain the differences in photoreaction rate, several factors such as distance between double bonds, best π-orbital overlap of the reacting C=C double bonds, and CSA tensor analysis (using 2D PASS) were taken into account. Calculations of 13C chemical shifts and chemical shift anisotropy tensor parameters show very good agreement with experimental data, including the carboxylic carbon that is hydrogen bonded to the neighboring cinnamic acid molecule. For the cinnamic acid photodimerization, the best angle between reacting double bonds and the smallest degree of molecular reorientation favor faster photoreaction.

Original languageEnglish (US)
Pages (from-to)12212-12218
Number of pages7
JournalJournal of Physical Chemistry C
Volume116
Issue number22
DOIs
StatePublished - Jun 7 2012

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Chemical shift
tensor analysis
Tensors
chemical equilibrium
Substitution reactions
Nuclear magnetic resonance
substitutes
Derivatives
solid state
nuclear magnetic resonance
acids
Kinetics
Acids
kinetics
Crystal structure
Bromine
crystal structure
bromine
Discrete Fourier transforms
Nuclear magnetic resonance spectroscopy

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

Cite this

Effects of aromatic substitution on the photodimerization kinetics of β-trans cinnamic acid derivatives studied with 13C solid-state NMR. / Fonseca, Isa; Baias, Maria; Hayes, Sophia E.; Pickard, Chris J.; Bertmer, Marko.

In: Journal of Physical Chemistry C, Vol. 116, No. 22, 07.06.2012, p. 12212-12218.

Research output: Contribution to journalArticle

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AB - In our efforts to study photodimerizations in the solid state, we present data on the influence of the position of aromatic substitution by bromine on the photodimerization rate in cinnamic acid derivatives. Results were obtained by 13C CPMAS NMR spectroscopy together with chemical shift tensor analysis, DFT calculations using the NMR-CASTEP program, and crystal structure data. Reaction rates are highest for para bromo substitution, whose parent crystal structure was solved in this work. To explain the differences in photoreaction rate, several factors such as distance between double bonds, best π-orbital overlap of the reacting C=C double bonds, and CSA tensor analysis (using 2D PASS) were taken into account. Calculations of 13C chemical shifts and chemical shift anisotropy tensor parameters show very good agreement with experimental data, including the carboxylic carbon that is hydrogen bonded to the neighboring cinnamic acid molecule. For the cinnamic acid photodimerization, the best angle between reacting double bonds and the smallest degree of molecular reorientation favor faster photoreaction.

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