Hydrophobic/Hydrophilic Interplay in 1,2,4‐Triazole‐ or Carboxylate‐Based Molybdenum(VI) Oxide Hybrids: a Step Toward Development of Reaction‐Induced Self‐Separating Catalysts

2-(4H-1,2,4-triazol-4-yl)acetic acid (trglyH) and (dl)-4-methyl-2-(4H-1,2,4-triazol-4-yl)pentanoic acid (trleuH) were used as ligands for the development of MoO3 coordination hybrids for catalytic applications. Coordination polymers [Mo2O6(Htrgly)] . H2O (1) and [MoO3(trleuH)] . 0.5H(2)O (2) were prepared and structurally characterized. Compound 1 adopts a structure in which edge-sharing MoO6 octahedra are organized in a ribbon motif via mu(3)-O bridges. The Htrgly ligand exists as a zwitterion: -CO2- links two Mo-VI in a mu(2)-eta(1) : eta(1) mode, while positively charged triazolium is left uncoordinated. In 2, Mo atoms are joined in a chain through mu(2)-O. The more hydrophobic trleuH appears in a nonionized form and its [N-N] sites serve as a "clamp" for supporting the [-OMo(O)(2)-OMo(O)(2)(tr)(2)](n) sequence. The complexes were explored for liquid phase catalytic epoxidation of cis-cyclooctene, using H2O2 or tert-butylhydroperoxide as oxidants. The hybrids showed good catalytic activity, and 2 behaved as a reaction-induced self-separating catalyst for olefin epoxidation with H2O2, presenting advantages of homogeneous and heterogeneous catalysis.