Preparation and characterization of lanthanide-azo-dye coordination polymers and polymer thin films via layer-by-layer depositions

A series of tartrazine-lanthanide dye compounds has been synthesized and characterized. Structural studies reveal that the light rare-earth elements La, Ce, Pr and Nd form coordination compounds with tartrazine ligands in a 1 : 1 ratio and result in 1-D 'fish-bone' chain-like structures having uncoordinated organosulfonate groups on each side of the chain. However, reactions of tartrazine and heavy rare-earth elements Ho, Er, Tm and Yb, in the presence of auxiliary 1,10-phenanthroline, give new 1-D coordination polymers in which uncoordinated organosulfonate groups are located on the same side of the chains. The tartrazine ligands display similar but slightly different coordination modes in both types of structures and the 1,10-phenanthroline plays a vital role in the formation of heavy rare-earth dye compounds. Based on the knowledge of their structures, the light rare-earth dye compounds were utilized to assemble with positively-charged PEI into multilayer thin films by means of layer-by-layer depositions. The as-synthesized thin films showed enhanced stability and consistency on solid surfaces.