Metal–Organic Coordination Network Thin Film by Surface-Induced Assembly

Abstract

The growth of metal-organic coordination network thin films on surfaces has been pursued extensively and intensively to manipulate the molecular arrangement. For this study, the oriented multilayer thin films based on porphyrinic nanoarchitecture were synthesized toward metal-organic coordination networks using surface-induced assembly (SIA). Nanoscale molecular thin films were prepared at room temperature using cobalt(II) ion and porphyrin building blocks as precursors. Stepwise growth with a highly uniform layer was characterized using UV-vis, AFM, IR, and XPS studies. The grazing incidence small-angle X-ray scattering and X-ray reflectivity results remarkably suggested a periodic structure in in-plane direction with constant and high mass density (ca. 1.5 g/cm(3)) throughout the multilayer formation. We propose that orientation of the porphyrin macrocycle plane with a hexagonal packed model by single anchoring mode was tilted approximately 60° with respect to the surface substrate. It is noteworthy that the well-organized structure of porphyrin-based macrocyclic framework on the amine-terminated surface substrate can be achieved efficiently using a simple SIA approach under mild synthetic conditions. The synthesized thin film provides a different structure from that obtained using bulk synthesis. This result suggests that the SIA technique can control not only the film thickness but also the structural arrangement on the surface. This report of our research provides insight into the ordered porphyrin-based metal-organic coordination network thin films, which opens up opportunities for exploration of unique thin film materials for diverse applications.

Docking MOF crystals on graphene support for highly selective electrocatalytic peroxide production

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Recent advances in hybrid measurement methods based on atomic force microscopy and surface sensitive measurement techniques

“…Here, the obtained amplitudes are related to the strength of the cantilever oscillation. Studies utilizing PTIR have analyzed the chemical information of biological samples, such as proteins, 279,280 lipids and lipid vesicles, 281,282 cells, 283,284 bacteria, 48,279,285 polymer samples and thin lms, 49,286-288 medical devices, 289 drugs, 290,291 nanostructures, [292][293][294] metal-organic frameworks (MOFs), 295 organo-halide perovskites, 296,297 and nano-patterned metals 298 at a resolution up to 50 nm. Here the improved resolution of the PTIR serves to analyze nanoscale regions of relatively thin samples.…”

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