The photodimerisation of trans-cinnamic acid and its derivatives: a study by vibrational microspectroscopy

Infrared and Raman spectroscopies have been used to monitor the 2 + 2] photodimerisation reactions of alpha-trans-cinnamic acid and of a number of its derivatives. The principal changes observed in the spectra upon dimerisation are decay of a band around 1637 cm(-1), which is assigned to v(C=C) of the ethene bond of the monomer, and growth of bands just above 3000 cm(-1), which result from v(C-H) of saturated carbon atoms of the dimer. The use of microscope attachments has allowed us to follow the reactions of single crystals and we conclude that the reactions are topotactic in nature. We have carried out preliminary kinetic experiments in which spectra of one single crystal are recorded after sequential periods of photolysis. We find that the rates of dimerisation of differently substituted cinnamic acids are similar, with physical effects, such as the thickness of an individual crystal, outweighing any observed electronic effects (inductive or mesomeric).