An analysis of compression isotherms of floating layers of copper tetra-tert-butylphthalocyanine (CuPctBu4) and copper tetrabenzotriazaporphyrine, obtained at varied initial conditions, is carried out. The structure of layers is determined by three methods: the traditional one (direct estimation of area per molecule from a π-A isotherm), by a quantitative analysis of compression isotherms (with the use of Volmer equation), and by Brewster angle microscopy. It is shown that in layers with edgeon arrangement of molecules (initial surface concentrations N 0 > 0.15 μmol.m -2 ), the layer structure, determined by the quantitative method, may differ drastically from the structure obtained by the traditional one. The equation of state of the floating layer generalized to the case when structural units of 2D gas are molecular aggregates is used to describe the layer of azaporphyrines. Boundaries of existence and characteristics of structure and properties of floating layers in stable states (size of nanoaggregates formed in a layer, number of molecules in them, interaggregate spacing, compressibility) are determined. The quantitative model of floating layer of copper tetra-tert-butylphthalocyanine is proposed. Constants characterizing a stable monolayer, as well as the region where it may be formed, are determined on the base of the model created.

An influence of copper cation in the complex on structure and properties of the floating layers of 5,10,15-triphenylcorrole (Cu[(ms-Ph) 3 Cor]) at the air-water interface was studied. The structure of the layers has been determined using the method of quantitative analysis of compression isotherms. A model of stable nanostructured layers of the substance has been constructed. Copper cation in the macrocycle increases the density of two-dimensional M-nanoaggregates, while the number of molecules in such aggregates experiences 2-3-fold growth. Like the metal-free triphenylcorrole, this copper-containing compound in multilayer Langmuir-Schaeffer (LS) films with edge-on arrangement of molecules forms aggregates with strong intermolecular interactions. Such LS films may be suitable for electrocatalysis in the oxygen reduction reaction.