Analysis of inter-ring coupling effects in N-heterobicyclic π-systems using a structural definition of aromaticity

A purely structural definition of aromaticity based on the average ring bond length and -bond order is proposed. The definition is illustrated for N-heterocycles by reference to theoretical STO-3G and 3-21G geometries and charges for some pteridine derivatives. The treatment focuses on the gross structural changes (i.e., ring size, overall degree of π-electron delocalization, and net ring charges), accompanying chemical changes, such as substitution, tautomerization, ring reduction, and deazination, as well as the structural interdependence of the two rings in a bicyclic ring system.