Following UV photoexcitation, organic diazo compounds can eliminate N$_{2}$ by C=N bond dissociation to form highly reactive singlet carbene intermediates. In solution, these carbenes rapidly react with nucleophilic solvents such as alcohols or ethers to form zwitterionic ylides. If the starting molecules are $\alpha$-diazocarbonyl compounds (with a carbonyl group adjacent to the diazo...
The mechanism of newly discovered photochemical reactions of $\beta$-enaminones and maleimide derivatives is a topic of interest and ongoing discussion [1,2]. We have examined excited-state dynamics in these systems following femtosecond UV excitation by means of ultrafast transient absorption spectroscopy with dispersed, broadband probing, complemented by the tools of computational...
We report on the state-of-the-art time-resolved photoelectron spectroscopy (LJ-TRPES) of molecular chromophores solvated in aqueous environment using wavelength-selected XUV pulses from high-order harmonic generation and micro-liquid jet (LJ) technology. LJ-TRPES is one of the most direct analytic methods to follow transient electronic structures of complex photoexcited molecules.
In one...
We re-visit the ligand exchange dynamics in Fe(CO)$_5$ , a textbook example of fluxionality or Berry pseudo rotation, by high-resolution polarization-dependent 2D-IR spectroscopy. Coupling maps at short waiting times reveal detailed information about the anharmonic structure: a very small negative coupling between the IR-active CO stretch modes A2′′ and E′ and distinct diagonal and...
