Metal mediated coordination polymers offer the opportunity to fabricate devices and materials that are equally important for fundamental research and new technologies. Most coordination polymers were synthesized at the desired stoichiometry. We demonstrate that coordination polyelectrolytes can form in layer-by-layer (LBL) assembled films regardless of the initial metal to bisligand ratio in solution. Upon dipping a substrate alternately into a covalent polylectrolyte solution and then into the mixed solution of Fe3+ and bisligands, the Fe3+ to ligand ratio in the LBL film tends to be 1:1 and forms polymeric structures even if the ratios in the bulk solution strongly deviate from unity. Our results suggest that layer-by-layer assembly promotes the formation of coordination polyelectrotyes.
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