Rational and site-selective formation of coordination polymers consisting of d10 coinage metal ions with thiolate ligands using a metal ion-doped polymer substrate.

Here, we report an interfacial approach for fabricating coordination polymers (CPs) consisting of d10 coinage metal ions with thiolate ligands on a polymer substrate. It was found that CPs were selectively formed on the polymer substrate, resulting in the formation of CP-based thin films. In addition, utilizing a mixed metal ion-doped polymer substrate leads to the formation of mixed-metal CP-based films.

Formation of Metal-Organic Frameworks on a Metal Ion-Doped Polymer Substrate: In-Depth Time-Course Analysis Using Scanning Electron Microscopy.

The growth of metal-organic frameworks (MOFs) on a metal ion-doped polymer as a precursor and support substrate was investigated based on mechanistic and kinetic analyses. The studies were performed by varying the reaction temperature and the concentrations of the organic ligand and nucleation-promoted additive. Using the NH2-MIL-53(Al) framework as a model system, a systematic study of the mechanism of formation of tetragonal- and rod-shaped NH2-MIL-53(Al) crystals on the substrate was performed. The nucleation rate in the early stage of the reaction is a major factor in determining the surface morphology of the resultant NH2-MIL-53(Al) crystal films, as confirmed by changing the concentration of organic ligands and by employing pyridine additives. These results provide a fundamental understanding of the influence of the nucleation rate on the ability to control the morphology and structure of MOF crystal films.