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The formation of ultrathin films of Rh-based porous metal-organic polyhedra (Rh-MOPs) by the Langmuir-Blodgett method has been explored. Homogeneous and dense monolayer films were formed at the air-water interface either using two different coordinatively alkyl-functionalized Rh-MOPs (HRhMOP(diz) 12 and HRhMOP(oiz) 12 ) or by in situ incorporation of aliphatic chains to the axial sites of dirhodium paddlewheels of another Rh-MOP (OHRhMOP) at the air-liquid interface. All these Rh-MOP monolayers were successively deposited onto different substrates in order to obtain multilayer films with controllable thicknesses. Aliphatic chains were partially removed from HRhMOP(diz) 12 films post-synthetically by a simple acid treatment, resulting in a relevant modification of the film hydrophobicity. Moreover, the CO 2 /N 2 separation performance of Rh-MOP-supported membranes was also evaluated, proving that they can be used as selective layers for efficient CO 2 separation.

Influence of the Surface Chemistry of Metal–Organic Polyhedra in Their Assembly into Ultrathin Films for Gas Separation