Morphology and orientation change of layer-by-layer deposited one- and two-dimensional coordination polymer nanocrystals containing rhodium paddle-wheel units

Abstract

Surface-directed and preferentially oriented assemblies of nanomaterials can enable enhanced applications in e.g. catalysis or sensing. Coordination polymers, which can be even conducting, could be suitable materials for this purpose because of their facile surface anchoring. Hence, we coassembled rhodium paddle-wheel building blocks with bi- or trifunctional linkers in dip coatings that were produced by layer-by-layer approach on silicon wafers functionalized by thin nanocrystalline gold surfaces. These gold surfaces were decorated with a self-assembled monolayer (SAM) for coordination and binding to the Rh-units. As linkers, pyrazine, triazine and melamine were used, leading to rectangularly-shaped, hexagonally-shaped or needle-like crystals, respectively. The coordination polymers were produced by repeated dipping into the linker and paddle-wheel solution, each followed by a cleaning step. The crystals growth was followed by atomic force microscopy (AFM) grazing incidence small-angle X-ray scattering (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS). AFM and GISAXS revealed the shape and size of the crystals. GIWAXS disclosed their preferred orientation. It turned out that the automated dipping procedure does not lead to a strong alignment of crystallites along the dipping direction for the pyrazine-based deposits. However, these crystals are preferentially oriented with respect to the substrate normal direction. The crystallographic direction and the degree of the alignment depend on the number of deposition cycles. In the early phases of the deposition process, predominantly “lying” crystals were detected. With increasing number of the deposition cycles, the fraction of “standing” crystals became dominant. These crystals are oriented with their {010} directions perpendicular to the surface of the substrate. Still, “lying” and some tilted crystals were detected additionally. The study gives a deeper structural understanding of crystallite assemblies and suggests an evolvement of more anisotropic orientations of the crystallites with increasing deposition cycles (leading to the prevalence of crystals having the preferred {010} orientation with respect to the surface normal direction).