Multinuclear ((1)H, (13)C, (95)Mo and (183)W) NMR spectroscopy, combined with DFT calculations, provides detailed information on the complexation between the Mo(VI) and W(VI) oxoions and 8-hydroxyquinoline-5-sulfonate (8-HQS) in aqueous solution. Over the concentration region studied, Mo(VI) and W(VI) oxoions form three homologous complexes with 8-HQS in water in the pH range 2-8. Two of these, detected at pH < 6, are mononuclear 1 : 2 (metal : ligand) isomers, with the metal centre (MO2(2+)) coordinated to two 8-HQS ligands. An additional complex, dominant at slightly higher pH values (5-8) for solutions with a 1 : 1 metal : ligand molar ratio, has a binuclear M2O5(2+) centre coordinated to two 8-HQS ligands. The two metal atoms are bridged by three oxygen atoms, two coming from 8-HQS, together with the M-O-M bridge of the bimetallic centre. We show that the long-range exchange corrected BOP functional with local response dispersion (LCBOPLRD), together with explicit solvent molecules, leads to geometries that readily converge to equilibrium structures having realistic bridging O8-HQS-M bonds. Previous attempts to calculate the structures of such binuclear complexes using DFT with the B3LYP functional have failed due to difficulties in treating the weak interaction in these bridged structures. We believe that the LCBOPLRD method may be of more general application in theoretical studies in related binuclear metal complexes. UV/visible absorption and luminescence spectra of all the complexes have also been recorded. The complex between Mo(vi) and 8-HQS is only weakly luminescent, in contrast to what has been observed with this ligand and many other metal ions. We suggest that this is due to the presence of low-lying ligand-to-metal charge transfer (LMCT) states close to the emitting ligand-based level which quench the emission. However, with W(VI), DFT calculations show that the LMCT states are now much higher in energy than the ligand based levels, leading to a marked increase in fluorescence.