A kinetically controlled trans bifunctionalized organoimido derivative of the Lindqvist-type hexamolybdate: synthesis, spectroscopic characterization, and crystal structure of (n-Bu4N)2{trans-[Mo6O17(NAr)2]} (Ar = 2,6-dimethylphenyl).

A kinetically controlled trans bifunctionalized organoimido derivative of hexamolybdate, (n-Bu(4)N)(2){trans-[Mo(6)O(17)(NAr)(2)]} (Ar = 2,6-dimethylphenyl) 1, in which the two 2,6-dimethylphenylimido groups are bonded to hexamolybdate at the trans positions, has been successfully synthesized in ca. 60% yield under mild reaction conditions. Its trans structure has been confirmed by a single-crystal X-ray diffraction study. In the crystals, cluster anions of 1 self-assemble into a 3D netlike structure via two different kinds of C-H...O hydrogen bondings, in which 1D supramolecular rectangular channels containing tetrabutylammonium cations form along the a axis. Compound 1 has also been characterized by (1)H NMR, IR, and UV-vis spectroscopic studies. UV-vis-near-IR reflectance spectroscopy measurements reveal the compound's nature of semiconductivity with an optical energy gap of 2.55 eV.