A Kinetically Controlled Trans Bifunctionalized Organoimido Derivative of the Lindqvist-Type Hexamolybdate:Synthesis,Spectroscopic Characterization,and Crystal Structure of (n-Bu_4N)_2{trans-[Mo_6O_(17)(NAr)_2]} (Ar=2,6-dimethylphenyl)

摘要

A kinetically controlled trans bifunctionalized organoimido derivative of hexamolybdate,(n-Bu_4N)_2{trans-[Mo_6O_(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 ~1H 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.