Unveiling the origin of photo-induced enhancement of oxidation catalysis at Mo(VI) centres of Ru(II)–Mo(VI) dyads

Photo-induced oxidation-enhancement in biomimetic bridged Ru(II)–Mo(VI) photo-catalyst is unexpectedly photo-activated in ps timescales. One-photon absorption generates an excited state where both photo-oxidized and photo-reduced catalytic centres are activated simultaneously and independently

Two-dimensional ultrafast transient absorption spectrograph covering deep-ultraviolet to visible spectral region optimized for biomolecules

We report on the implementation of a multi-kHz single-shot referenced non-coherent two-dimensional UV spectrograph based on conventional pump-probe geometry. It has the capability to cover a broad spectral region in excitation from 270-to-380 nm and in the detection from 270-to-390 nm and 320-to-720 nm. Other setups features are: an unprecedented time resolution of 33 fs (standard deviation); signals are photometrically corrected; a single shot noise of <1 mOD. It has the capability to operate with sample volumes as small as few μl which is an accomplishment in studying biological or biomimetic systems. To show its performances and potentials, we report two preliminary studies on the photophysics of phenanthrenes hosted in a multichromophoric antenna system and of aromatic amino acids in a blue-copper azurin

Energy and charge transfer dynamics in DNA based light harvesting antennae

DNA can serve as a versatile scaffold for chromophore assemblies. For example, light-harvesting antennae have been realized by incorporating phenanthrene and pyrene building blocks into DNA strands. It was shown that by exciting at 320 nm (absorption of phenanthrene), an emission at 450 nm is observed which corresponds to a phenanthrene-pyrene exciplex. The more phenanthrenes are added into the DNA duplex, the higher is the fluorescence intensity with no significant change in quantum yield. This shows that phenanthrene acts as a donor and efficiently transfers the excitation energy to the pyrene. Up to now, the mechanism of this energy transfer and exciplex formation is not known. Therefore, we first aim at studying the photo-cycle of such DNA assemblies through transient absorption spectroscopy. Based on the results, we will explore ways to manipulate the energy transfer by application of intense THz fields. Ground as well as excited state Stark effect dynamics will be investigated

Ultrafast dynamics in polycyclic aromatic hydrocarbons: the key case of conical intersections in higher excited states and their role in the photophysics of phenanthrene monomer✝

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