ИСТИНА

Coordination polymers composed of porphyrins and metal ions provide an enlightening example of supramolecular synthesis for fabricating multichromophoric arrays for various applications. Herein, we report a new strategy of self-assembly of 2D coordination networks in Langmuir monolayers. Unlike common approach, our strategy uses metal-free tetrapyridyl porphyrin as a primary building unit instead of metal complex of this ligand. This approach relies on the interactions of metal ions both with peripheral groups and with a central cavity to achieve periodically ordered structure of 2D multiporphyrin arrays with face-on orientation of macrocycles. We found that the control of metalation-demetalation processes of porphyrin ring is a key factor for both formation of 2D multiporphyrin arrays and their further transformation into SURMOFs. For the monolayer at the air/water interface, the incorporation of zinc into the porphyrin ring requires a considerably longer time as well as higher concentration of salt in the subphase, when compared to similar reaction in bulk solution. Zinc ions boost the fluorescence of TPyP in organic solvent, whereas their presence in the subphase under the monolayer of TPyP results in fluorescence quenching. Uniformity of the networked films formed on Zn-containing subphase and deposited on solids was demonstrated by SEM and AFM techniques.