Driving Coordination Polymer Monolayer Formation by Competitive Reactions at the Air/Water Interface

We have developed a novel approach enabling us to follow and facilitate the formation of two-dimensional coordination polymer monolayers directly at the air/water interface without the need of complex instrumentation. The method is based on the use of a surface active ligand that, when spread at the air/water interface, progressively undergoes hydrolysis with consequent gradual decrease in surface pressure. Notably, if the aqueous subphase contains metal ions capable of coordinating the ligand, coordination competes with hydrolysis, resulting in a lower surface pressure decrease. As a consequence, the formation of the coordination polymer monolayer can be verified simply by surface pressure measurements. Competition between hydrolysis and coordination was investigated as a function of the main experimental parameters affecting the two reactions, enabling the formation of stable coordination polymer monolayers with controlled density. Finally, the formation of continuous rigid 2D layers was confirmed by compression isotherms and ex situ morphological characterization. This work will simplify the verification of coordination polymer monolayer formation; thus, it will boost the synthesis of novel and innovative 2D materials.