ABSTRACT
Small anionic nickel clusters with ethanol are investigated with a combination of mass-selective infrared photodissociation spectroscopy in a molecular beam and density functional theory simulations at the BLYP/6-311g(d,p) and TPSSh/def2-TZVPP level. In this context, the O-H stretching vibration of the ethanol is analyzed to obtain information about the structural motif, the geometry of the metal core, and the spin state of the clusters. For the [Ni2(EtOH)]- and [Ni3(EtOH)]- clusters, we assign quartet states of motifs with a hydrogen bond from the ethanol to the linear nickel core. The aggregation of a further ethanol molecule, yielding the [Ni3(EtOH)2]- cluster, results in the formation of a cooperative hydrogen bond network between the nickel core and the two ethanol molecules.
ABSTRACT
A detailed theoretical and spectroscopic study on the electronically excited states of a trinuclear palladium complex is presented both in the gas phase and solution. The application of DFT and TDDFT methods as well as a variety of spectroscopic methods to the chosen complex [Pd3{Si(mt(Me))3}2] (1, mt(Me) = methimazole) leads to the first detailed analysis of the photophysics of a symmetric trinuclear complex. In combination with the calculations, energies, structures and lifetimes of the excited electronic states (with an (3)A1 state as the lowest one) are characterized by applying the resonant-2-photon-ionization method in a molecular beam experiment as well as luminescence, time-correlated single photon counting and excited state femtosecond absorption spectroscopy in solution. These investigations are of fundamental interest to analyze photophysical properties of metal containing complexes on a molecular level.
