ИСТИНА

Fabricating of solid-supported porphyrin-based metal organic networks which are a new class of functional porous materials promising for various applications remains a challenging problem for supramolecular chemistry. Surface-directed assembly of molecules and nanosized objects offers a labile platform for tailoring solid surfaces with well-defined supramolecular and hybrid assemblies presenting various functionalities. Several examples enlightening the application of this concept to the fabrication of stable surface-attached metal organic frameworks (SURMOFs) as films on planar solid supports as well as on dispersed solid particles will be discussed. One of them shows that SURMOFs can be assembled from variously substituted zinc porphyrins or PDI derivatives as linkers on surfaces, decorated with graphene oxide (GO).[1, 2] Because the microscopically flat 2D carbon template initiate the growth of macroscopically uniform SURMOF films (Fig.1a), they exhibited both well-resolved X-ray diffraction and angle dependence of fluorescence making it possible to determine the relation between the structure of linkers and the packing motives in the films (Fig.1b). The surface effect manifests itself as different packing of SURMOFs in bulk and in 2D space due to steric limitations, whereas the coordination motive dictates the morphology of SURMOFs. Another approach was used to fabricate catalytically active supramolecular hybrids on colloidal templates: (i) the porphyrin-based SURMOF/GO composites obtained in the Pickering emulsions, and (ii) a synergetic catalyst assembled from ZnTCPP and zinc acetate on the particles of layered europium hydroxochloride as anion-exchange 2D template. A combination of methods including MALDI-TOF spectroscopy was exploited for understanding the origin of synergetic effects and the mechanisms of catalysis in these solid-associated supramolecular hybrids. These strategies provide a basis for new types of self-assembled coordination structures on solid matrices suitable for their integration with modern planar technologies in chemical sensing, optics, molecular electronics and catalysis.