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From the reactions between M 2 (T  i  PB) 4 compounds and meta and para - vinylbenzoic acids (2 equiv) in toluene at room temperature the compounds trans -M 2 (T  i  PB) 2 L 2 , where L = m -vinylbenzoate 1A (M = Mo) and 1B (M = W) and T  i  PB = 2,4,6-triisopropylbenzoate, and where L = p -vinylbenzoate 2A (M = Mo) and 2B (M = W) have been isolated. Compounds 1A and 2A have been shown to undergo Heck carbon-carbon coupling reactions with phenyliodide to produce trans -Mo 2 (T  i  PB) 2 (O 2 CC 6 H 4 - m -CH=CH-C 6 H 5 ) 2,  3A and trans -Mo 2 (T  i  PB) 2 (O 2 CC 6 H 4 - p -CH=CH-C 6 H 5 ) 2 , 4A . The molybdenum compounds 1A and 2A have been structurally characterized by single crystal X-ray crystallography. All the new compounds have been characterized by 1 H NMR, IR, UV-Visible absorption and emission spectroscopy, high resolution MALDITOF MS, fs- and ns- transient absorption spectroscopy and fs- time-resolved IR spectroscopy. Electronic structure calculations employing density functional theory, DFT, and time-dependent DFT have been employed to aid in the interpretation of spectral data. All compounds show intense absorptions in the visible region corresponding to M 2 δ to Lπ* charge transfer transitions. The lifetimes of the 1 MLCT state fall in the range of 1 - 10 ps and for the molybdenum complexes the T 1 states are 3 δδ* with lifetimes ~50 μs while for the tungsten complexes the T 1 are 3 MLCT with lifetimes in the range of 3 - 10 ns.

MM quadruply bonded complexes supported by vinylbenzoate ligands: synthesis, characterization, photophysical properties and application as synthons