Facile Synthesis of 3-(Azol-1-yl)-1-adamantanecarboxylic Acids—New Bifunctional Angle-Shaped Building Blocks for Coordination Polymers.

For the first time, orthogonally substituted azole-carboxylate adamantane ligands were synthesized and used for preparation of coordination polymers. The angle-shaped ligands were prepared by the reaction of 1-adamantanecarboxylic acid and azoles (1H-1,2,4-triazole, 3-methyl-1H-1,2,4-triazole, 3,5-dimethyl-1H-1,2,4-triazole, 1H-tetrazole, 5-methyl-1H-tetrazole) in concentrated sulfuric acid. Variation of the solvent and substituents in azole rings allowed to prepare both 1D and 2D copper(II) and nickel(II) coordination polymers, [Cu₂(trzadc)₄(H₂O)_0.7]∙DMF∙0.3H₂O, [Cu(trzadc)₂(MeOH)]∙MeOH, [Ni(trzadc)₂(MeOH)₂] and [Cu₂(mtrzadc)₃(MeOH)]⁺NO₃^– (trzadc-3-(1,2,4-triazol-1-yl)-adamantane-1-carboxylic acid; mtrzadc-3-(3-methyl-1,2,4-triazol-1-yl)-adamantane-1-carboxylic acid) which were structurally characterized by single crystal X-ray diffraction. Complex [Cu(trzadc)₂(MeOH)]∙MeOH was shown to act as a catalyst in the Chan-Evans-Lam arylation reaction. [ABSTRACT FROM AUTHOR]