Multinuclear solid-state magnetic resonance study of oxo-bridged diniobium and quadruply-bonded dimolybdenum...

Carboxylate paddlewheels and their oxo-bridged analogues constitute ideal building blocks for the assembly of two- and three-dimensional framework materials. Here, we present a multinuclear (¹H, ¹³C, ⁹³Nb, ⁹⁵Mo) magnetic resonance study of solid samples of Nb₂OCl₆(O₂Ph)₂ (1), Mo₂(O₂CMe)₄ (2), and Mo₂(O₂CCHF₂)₄ (3). High-resolution proton and ¹³C CP/MAS NMR spectra provide valuable information on structure and crystal symmetry and on cocrystallized solvent. ⁹³Nb solid-state NMR spectra of 1 provide quadrupolar coupling constants and chemical shift tensors which are characteristic of the axially asymmetric Nb-O-Nb bridging environment. ⁹⁵Mo solid-state NMR spectra of 2 and 3 provide quadrupolar coupling constants and chemical shift tensors which are directly characteristic of the molybdenum-molybdenum quadruple bonds in these compounds. The quadruple bonds are characterized by particularly large ⁹⁵Mo chemical shift tensor spans on the order of 5500ppm. Density functional theoretical computations provide good agreement with the ⁹³Nb and ⁹⁵Mo experimental data, with some exceptions noted. This work demonstrates possible NMR approaches to characterize more complex framework materials and provides key insight into the Mo-Mo quadruple bond.