Time-Resolved Spectroscopy of Photoinduced Electron Transfer in Dinuclear and Tetranuclear Fe/Co Prussian Blue Analogues.

The dynamics of the photodriven charge transfer-induced spin transition (CTIST) in two Fe/Co Prussian Blue Analogues (PBAs) are revealed by femtosecond IR and UV/vis pump-probe spectroscopy. Depending on temperature, the known tetranuclear square-type complex [CoFe(CN)(tp*)(4,4'-dtbbpy)](PF) () exists in two electronic states. In acetonitrile solution, at <240 K, the low temperature () phase is prevalent consisting of low-spin Fe(II) and low-spin Co(III), [FeCo].

Competing H versus Intramolecular C-H Activation at a Dinuclear Nickel Complex via Metal-Metal Cooperative Oxidative Addition.

Nickel(I) metalloradicals bear great potential for the reductive activation of challenging substrates but are often too unstable to be isolated. Similar chemistry may be enabled by nickel(II) hydrides that store the reducing equivalents in hydride bonds and reductively eliminate H upon substrate binding. Here we present a pyrazolate-based bis(β-diketiminato) ligand [L] with bulky -terphenyl substituents that can host two Ni-H units in close proximity.

Tailoring Ru(II) pyridine/triazole oxygenation catalysts and using photoreactivity to probe their electronic properties.

Tuning of ligand properties is at the heart of influencing chemical reactivity and generating tailor-made catalysts. Herein, three series of complexes [Ru(L)(Cl)(X)]PF6 (X=DMSO, PPh3 , or CD3 CN) with tripodal ligands (L1-L5) containing pyridine and triazole arms are presented. Triazole-for-pyridine substitution and the substituent at the triazole systematically influence the redox behavior and photoreactivity of the complexes.