MOF‐on‐MOF: Oriented Growth of Multiple Layered Thin Films of Metal–Organic Frameworks

Abstract The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF‐on‐MOF films, over macroscopic length scales is presented. The MOF‐on‐MOF films are fabricated by epitaxially matching the interface. The first MOF layer (Cu 2 (BPDC) 2 , BPDC=biphenyl‐4,4′‐dicarboxylate) is grown on an oriented Cu(OH) 2 film by a “one‐pot” approach. Aligned second (Cu 2 (BDC) 2 , BDC=benzene 1,4‐dicarboxylate, or Cu 2 (BPYDC) 2 , BPYDC=2,2′‐bipyridine‐5,5′‐dicarboxylate) MOF layers can be deposited using liquid‐phase epitaxy. The co‐orientation of the MOF films is confirmed by X‐ray diffraction. Importantly, our strategy allows for the synthesis of aligned MOF films, for example, Cu 2 (BPYDC) 2 , that cannot be grown on a Cu(OH) 2 surface. We show that aligned MOF films furnished with Ag nanoparticles show a unique anisotropic plasmon resonance. Our MOF‐on‐MOF approach expands the chemistry of heteroepitaxially oriented MOF films and provides a new toolbox for multifunctional porous coatings.