Self-assembled multilayers of transition-metal-terpyridinyl complexes; formation, and characterization

Layer-by-layer (LBL) growth of terpyridinyl ligands with a range of metal ions is reported. Monolayers of mercaptophenyl terpyridine on gold were used to initiate LBL assembly by complexing the first layer of metal ions. Tetra-2-pyridinylpyrazine was used as a linking ligand between subsequent metal ion layers. The assembly of the terpyridines with 21 different metals was evaluated using UV absorbance spectroscopy, variable-angle spectroscopic ellipsometry, and atomic force microscopy. Successful LBL growth appears to depend on the ionic radius of the metal ion. Metals that formed multilayered LBL structures were primarily limited to a small range of effective ionic radii between 66 and 73 pm. Metal ions with smaller ionic radii usually formed initial layers but seldom exhibited consistent LBL growth, while ions with radii larger than 73 nm generally did not demonstrate any evidence of LBL growth.