Quadruply bonded dimetal units supported by 2,4,6-triisopropylbenzoates MM(TiPB) 4 (MM = Mo 2, MoW, and W 2): Preparation and photophysical properties

Brian G. Alberding, Malcolm H. Chisholm, Yi Hsuan Chou, Judith C. Gallucci, Yagnaseni Ghosh, Terry L. Gustafson, Nathan J. Patmore, Carly R. Reed, Claudia Turro

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The preparation and characterization (elemental analysis, 1H NMR, and cyclic voltammetry) of the new compounds MM(TiPB) 4, where MM = MoW and W 2 and TIPB = 2,4,6-trilsopropylbenzoate, are reported. Together with Mo 2(TiPB) 4, previously reported by Cotton et al. {Inorg. Chem. 2002, 41, 1639), the new compounds have been studied by electronic absorption, steady-state emission, and transient absorption spectroscopy (femtosecond and nanosecond). The compounds show strong absorptions In the visible region of the spectrum that are assigned to MMo to arylcarboxylate π* transitions, 1MLCT. Each compound also shows luminescence from two excited states, assigned as the 1MLCT and 3MMδδ* states. The energy of the emission from the 1MLCT state follows the energy ordering MM = Mo 2 > MoW > W 2, but the emission from the 3MMδδ* state follows the Inverse order: MM = W 2 > MoW > Mo 2. Evidence Is presented to support the view that the lower energy emission in each case arises from the 3MMδδ* state. Lifetimes of the 1MLCT states in these systems are ∼0.4-6 ps, whereas phosphorescence is dependent on the MM center: Mo 2 ∼ 40 fis, MoW ∼ 30 μs, and W 2 ∼ 1 μs.

Original languageEnglish
Pages (from-to)4394-4399
Number of pages6
JournalInorganic Chemistry
Issue number10
Early online date20 Apr 2009
Publication statusPublished - 18 May 2009
Externally publishedYes


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