The Metal–Organic Framework, [Ni2(dhtp)] (H4dhtp = 2,5-dihydroxyterephthalic acid) was modified by gas-phase grafting of Mo(CO)6 at the gram-scale via a post-synthesis modification approach. A highly dispersed well-defined bimetallic material containing the [Ni2(dhtp)Mo(CO)3] fragment either in the staggered or in the eclipsed conformation was obtained, with a maximum coverage of 50%mol, as shown by multitechnique characterization: IR (diagnostic ν(CO) = 1996, 1972, 1926, 1885, and 1797 cm–1), N2 adsorption (Brunauer–Emmett–Teller (BET) surface area = 172 m2 g–1, pore volume 0.1 cm3/g), elemental analyses (Ni = 21.6%wt, Mo = 9.6%wt), mass balanced analyses of evolved gases (3.0 ± 0.2 mols of CO evolved/mol of grafted Mo(CO)6 high-resolution transmission electron microscopy (HRTEM). The staggered conformer is stabilized by an intermolecular Ni···(OC)Mo interaction with the framework open Ni(II) site, which causes the markedly blue-shifted stretching band observed at ν(CO) = 1797 cm–1. Upon decomposition in...