Detection of the Singlet and Triplet MM δδ* States in Quadruply Bonded Dimetal Tetracarboxylates (M = Mo, W) by Time-Resolved Infrared Spectroscopy

The compounds M(2)(O(2)C(t)Bu)(4) and M(2)(O(2)CC(6)H(5))(4), where M = Mo or W, have been examined by femtosecond time-resolved IR (fs-TRIR) spectroscopy in tetrahydrofuran with excitation into the singlet metal-to-ligand charge-transfer ((1)MLCT) band. In the region from 1500 to 1600 cm(-1), a long-lived excited state (>2 ns) has been detected for the compounds M(2)(O(2)C(t)Bu)(4) and Mo(2)(O(2)C-C(6)H(5))(4) with an IR absorption at ~1540 cm(-1) assignable to the asymmetric CO(2) stretch, ν(as)(CO(2)), of the triplet metal-metal δ-δ star ((3)MM δδ*) state. The fs-TRIR spectra of W(2)(O(2)C-C(6)H(5))(4) are notably different and are assigned to decay of the MLCT states. In (3)MM δδ*, the removal of an electron from the δ orbital reduces MM δ to CO(2) π* back-bonding and causes a shift of ν(as)(CO(2)) to higher energy by ~30-60 cm(-1), depending on the metal. TRIR spectroscopy also provides evidence for M(2)(O(2)C(t)Bu)(4), where M = Mo or W, having MM δδ* S(1) states with ν(as)(CO(2)) distinct from those of the (3)MM δδ* states.