Polymer Infiltration Into SURMOF Channels Enables Hydrophobic and Solid‐Like Slippery Functional Thin Films

ABSTRACT Designing functional thin films with precisely controlled surface chemistry and smoothness is essential for achieving targeted interfacial properties. Here, we introduce a polymer‐chain insertion strategy to fabricate pore‐threaded films by grafting uniformly long polymer chains into the vertical channels of surface‐mounted metal–organic frameworks (SURMOFs). Using the highly oriented pillared‐layer Cu 2 (bdc) 2 (dabco) SURMOF grown by layer‐by‐layer deposition as a crystalline host, infiltration of polymer chains into its nanochannels allows systematic tuning of interfacial chemistry and water wettability. Insertion of hydrophobic n‐alkane chains effectively masks the polar framework surface, enhances water stability, and imparts strong hydrophobicity. Polymer incorporation leads to characteristic modifications in the X‐ray diffraction pattern, and infrared spectroscopy reveals chain alignment through shifts in CH‐stretching modes. Notably, films infiltrated with long tetracontane (C 40 H 82 ) chains exhibit lubricant‐free slippery behavior, enabling water droplets to slide off readily due to the combination of smooth surface morphology and the low surface energy of exposed hydrocarbon segments. This scalable approach provides an internally integrated method for tailoring SURMOF thin‐film properties, expanding their applicability in liquid‐repellent coatings, anti‐fouling surfaces, and separation technologies.