167 research outputs found
Metal-Oxo Photo-oxidants, Photochemistry and Photophysics of trans-[Os^(VI)(tmc)(O)_2]^(2+)(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane) and trans-[Os^(VI)(CN)_4(O)_2]^(2-)
trans-[Os^(VI)(tmc)(O)_2]^(2+)(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane) and trans-[Os^(VI)(CN)_4(O)_2]^(2-) are emissive in the solid state and in fluid solutions at room temperature (τ~ 1.0–1.5 µs); the (^3)E_g state of trans-[Os^(VI)(tmc)(O)_2]^(2+) is a powerful one-electron oxidant {[Os^(VI)(O)_2]^(2+) + e^– → [Os^V (O)_2]+, E^0_f > 2.0 V vs. normal hydrogen electrode} in aqueous solution, reacting with PPh3 and ((PhCH_2)_2)S to give O=PPh_3 and ((PhCH_2)_2)S=O, respectively
High-valent ruthenium and osmium oxo complexes for homogeneous and photochemical oxidations of inorganic and organic substrates
published_or_final_versionChemistryDoctoralDoctor of Philosoph
Photo- and Temperature-Induced Reversible Structural Transformation between Dodecanuclear and Pentadecanuclear Gold(I) Sulfido Complexes
Stimuli-responsive structural transformation has attracted
much
attention for its potential to mimic the behavior of biological transformations
and functions. Here, two unprecedented dodecanuclear and pentadecanuclear
gold(I) sulfido clusters (denoted trans-Au12 and trans-Au15, respectively) with impressive stimuli-responsive
interconversion have been obtained by taking advantage of the judiciously
designed tridentate phosphine ligand Ltrans as the building block. Both UV light and temperature can be applied
to trigger the structural conversions between trans-Au12 and trans-Au15. In addition, NMR, high-resolution
electrospray ionization mass spectrometry, and UV–vis absorption
spectroscopy have been employed to monitor the transformation process
and decipher the mechanism of structural conversion. This work not
only provides a paradigm to investigate photo-induced cluster-to-cluster
transformation based on polydentate phosphine ligands but also offers
a new direction for the construction of the stimuli-responsive materials
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