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ISSN 1998-9539

Bilayer Porphyrin-Graphene Templates for Self-Assembly of Metal-Organic Frameworks on the Surface

E. V. Ermakova,a Yu. Yu. Enakieva,a I. N. Meshkov,a A. E. Baranchikov,b A. I. Zvyagina,a Yu. G. Gorbunova,a,b A. Yu. Tsivadze,a M. A. Kalinina,a and V. V. Arslanova@
aFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119071 Moscow, Russia
bKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia
@Corresponding author E-mail: vladimir.arslanov@gmail.com
 
DOI: 10.6060/mhc171259a
Macroheterocycles 2017 10(4-5) 496-504
 
Herein, we describe a new strategy for the formation of bilayer porphyrin-graphene templates to initiate the assembly of various organic or hybrid films including surface metal-organic frameworks on solid substrates. This strategy involves a one-step assembly of a bilayer from the ordered monolayer of functionalized porphyrin and the adsorption layer of graphene oxide at the air-water interface. The behavior of the monolayers of tetrapyridylporphyrin and tetracarboxylphenylporphyrin zinc complexes was studied on the surface of deionized water, aqueous solutions of zinc acetate, graphene oxide and graphene oxide in the presence of zinc acetate. By using a combination of the Langmuir surface method, in situ fiber optic UV-Vis absorption spectroscopy and fluorescence spectroscopy, we determined the molecular organization of the porphyrin films on surface of pure water. The effects of zinc cations and/or the adsorption layer of the graphene oxide on this organization were demonstrated. Strong interactions between the components of the bilayer lead to a substantial shift in the compression isotherms as well as to the quenching of the fluorescence of the porphyrins. The nature of the substituents in the porphyrin structure influences both the structure of the bilayer on the surface of liquid and the morphology of the bilayers transferred onto the solid substrate by the Langmuir-Blodgett technique. The most attractive aspect of our method is a screening of the structure of organic layer from the influence of the underlying solid surface by the GO layer, when the bilayer of tightly bound porphyrin and GO is transferred onto the solid substrate. Because of the specific properties of GO, the resulting bilayer is firmly anchored to the surface, which inhibits desorption of the bilayer material in a course of further bottom-up assembly via Langmuir-Blodgett technique or layer-by-layer assembly. One of the most important advantages of the proposed strategy is the opportunity for creating templates on solid substrates with different nature without use of self-assembled monolayers..

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