Ligand-to-ligand and ligand-to-metal charge transfer states are examined in new metallo-dichalcogenolene complexes with respect to understanding the electronic origin of the observed five member dichalcogenolene ring “envelope” fold distortion. We will present a combination of electronic absorption, resonance Raman, and EPR spectroscopies that directly probe the underpinning electronic structure requirements that are responsible for these fold-angle distortions. Our results are discussed in terms of a modified two-state vibronic coupling model, which can be used to effectively explain the electronic origin of an asymmetry in the ground state double potential well.  Our results suggest that similar vibronic instabilities may play an important role in modulating the electronic structure of metallo-dichalcogenolenes in general, and more specifically the electron and atom transfer reactivity observed in pyranopterin molybdenum enzymes.

Origin of ground state instability in new metallo-dichalcogenolenes

251st National Meeting (2016)

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