About Intermolecular Interaction,Submolecular Structure,and Paramagnetism of Polyconjugated Systems

It is shown that macromolecules with polyconjugated systems are capable of forming strong 7r-complex associates. The paramagnetic centers cause intercombinative transitions in auto- or α-complexes with other molecules and increase their reactivity (“effect of local activation”).

At the present time it has been determined that an increase of polyconjugated chains leads to a decrease of the energy slits and the energy of excited states.

At the same time ionization potentials (I) are decreased, but electron affinity (A) and electron polarizability are increased. One can show that the change of the difference I - A correlates with the change in the physicochemical properties of polyconjugated homologs 1,2]. Some data concerning aromatic hydrocarbons, wherein the polarization and space influence of groups and heteroatoms are excluded, may be illustrative.

As we can see from Figs. 1 and 2, in the cases of polyacene and poly-p-phenylene the melting points and the heat of sublimations increase with a decrease in I - A. At the same time the solubility and activation energy of conductivity of these compounds decrease.