3 years ago

Controlling Photochemistry via Isotopomers and IR Pre-excitation

Photochemistry via Isotopomers and IR
Daniela Kern-Michler, Nicole Mielke, Carsten Neumann, Alexander Heckel, Luuk J. G. W. van Wilderen, Jan von Cosel, Jens Bredenbeck, Irene Burghardt, Fabrizio Santoro, Matiss Reinfelds
It is a photochemist’s dream to be able to photoinduce a reaction of a specific molecular species in an ensemble of similar but not identical ones. The problem is that similar molecules often exhibit nearly identical UV–Vis absorption spectra, making them difficult or impossible to distinguish or to select spectroscopically. The ultrafast VIPER (VIbrationally Promoted Electronic Resonance) pulse sequence allows to pick a single species for electronic excitation based on its infrared spectrum. The latter usually shows more features, allowing the discrimination between species than the UV–Vis spectrum. Here, we show that it is possible to induce and monitor species-selective photochemistry even for molecules with virtually identical UV–Vis spectra, which is the case for isotopomers. Next to isotope-selective photochemistry in solution, applications to orthogonal photo-uncaging and species-selective spectroscopy and photochemistry in mixtures are within reach.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b08723

DOI: 10.1021/jacs.7b08723

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