Details

Autor(en) / Beteiligte

• Brown-Xu, Samantha E
• Chisholm, Malcolm H
• Gallucci, Judith C
• Ghosh, Yagnaseni
• Gustafson, Terry L
• Reed, Carly R

Titel

Furan- and selenophene-2-carboxylato derivatives of dimolybdenum and ditungsten (M[quadruple bond]M): a comparison of their chemical and photophysical properties

Ist Teil von

• Dalton transactions : an international journal of inorganic chemistry, 2012-02, Vol.41 (8), p.2257-2263

Ort / Verlag

England

Erscheinungsjahr

2012

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• From the reactions between M(2)(T(i)PB)(4), where T(i)PB = 2,4,6-triisopropylbenzoate and two equivalents each of 2-furan carboxylic acid, FuCO(2)H, and 2-selenophene carboxylic acid, SpCO(2)H in toluene, the new compounds trans-M(2)(T(i)PB)(2)(O(2)CFu)(2) (1a M = Mo, 2a M = W) and trans-M(2)(T(i)PB)(2)(O(2)CSp)(2) (1b M = Mo, 2b M = W) were formed. These new compounds have been characterized by (1)H NMR, steady-state UV-Vis-NIR absorption and emission spectroscopy, cyclic and differential pulse voltammetry, and fs and ns transient absorption spectroscopy. The compound Mo(2)(T(i)PB)(2)(O(2)CSp)(2) (1b) has been characterized by single crystal X-ray crystallography. These data are compared with those previously reported for related 2-thiophene carboxylate derivatives: M(2)(T(i)PB)(2)(O(2)CTh)(2). The physico-chemical data correlate well with electronic structure calculations performed on model compounds. All compounds have detectible S(1) photoexcited states with lifetimes that vary from ∼5 ps to < 1 ps. The molybdenum compounds have T(1) states with microsecond lifetimes that are assigned as MMδδ* whereas the T(1) states for tungsten are (3)MLCT with lifetimes on the order of nanoseconds. In all cases, shorter lifetimes were seen in complexes containing heavier atoms.