Convenient synthesis of tridentate 2,6-di(pyrazol-1-yl)-4-carboxypyridine and tetradentate 6,6′-di(pyrazol-1-yl)-4,4′-dicarboxy-2,2′-bipyridine ligands

Citrazinic acid is used as a convenient starting material for both tridentate 2,6-di(pyrazol-1-yl)-pyridine and tetradentate 6,6′-di(pyrazol-1-yl)-2,2′-bipyridine ligands containing carboxylic groups useful for further anchoring of sensitizer on TiO2 for dye-sensitized solar cells (DSCs). Using 2,6-dichloro-4-carboxypyridine, the synthesis of the terdentate ligands was improved compared to previously used 2,6-dibromo-4-carboxypyridine or 2,6-dichloro-4-ethylcarboxylate pyridine. Controlling the reaction conditions, it is possible to efficiently obtain the monosubstituted 2-chloro-6-pyrazol-1-yl-4-carboxypyridine, a key intermediate for the preparation of tetradentate 6,6′-di(pyrazol-1-yl)-4,4′-dicarboxy-2,2′-bipyridine ligand.