Metal-Ion Induced In Situ Ligand Oxidation for Self-Assembled Clusters: from Bis(5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl)methane to Alcohol or Ketone.

Hydrothermal reactions of metal nitrates and ligand bis(5-(pyridine-2-yl)-1,2,4-triazol-3-yl)methane (H₂L¹) gave three cluster compounds, {Cr₂}, {Zn₁₂} and {Fe₈}. Notably, methylene group of H₂L¹ was in situ oxidized either to hydroxymethylated (L²-O)³⁻ in the metallo-ring {Zn₁₂} or to a rigid carbonylated (L³=O)²⁻ in the screw-type {Fe₈}. In light of comparative experimental results, NO₃⁻ was deduced to be of a catalytic role in the ligand oxidation. Metal ion could be regarded as an 'induced' tool for clusters generation in self-assembly process. [ABSTRACT FROM AUTHOR]