Strain-Controlled Spin Transition in Heterostructured Metal-Organic Framework Thin Film

Metal-organic framework (MOF) thin films have recently attracted much attention as a new platform for surface/interface research, where unconventional structural and physical properties emerge. Among the many MOFs as candidates for fabrication of thin films, Hofmann-type MOFs {Fe(pz)[M(CN)₄]} [pz = pyrazine; M = Ni (Nipz), M = Pt (Ptpz)] are attractive, because they undergo spin transitions with concomitant structural changes. Here, we demonstrate the first example of a strain-controlled spin transition in heterostructured MOF thin films. The spin transition temperature ofPtpzcan be controlled in the temperature range of 300-380 K by fabricating a nanometer-sized heterostructured thin film with aNipzbuffer layer, where the smaller lattice ofNipzcauses epitaxial compressive strain to thePtpzlayer. The fabricated heterostructured thin film exhibited a remarkable increase in spin transition temperature with a dynamic structural transformation, confirmed by variable-temperature (VT) X-ray diffraction and VT Raman spectroscopy. By verifying interfacial strain in a heterostructured thin film, we can rationally control the characteristics of MOFs—not only spin transition but also various physical properties such as gas storage, catalysis, sensing, proton conductivity, and electrical properties, among others.