Supplementary Conjugated Circuits for Biphenylene and related hydrocarbons

TL;DR

This paper introduces supplementary conjugated circuits, S_1 and S_2, as key factors influencing the stability of biphenylene and related hydrocarbons, expanding the understanding of their resonance structures and energy corrections.

Contribution

The study identifies and theoretically predicts the role of new conjugated circuits, S_1 and S_2, in determining the stability of Kekule structures in biphenylene-like hydrocarbons.

Findings

S_1 and S_2 circuits contribute to energy corrections.

Structures with S_1 and S_2 are most stable.

Structures with double bonds between hexagonal rings are least stable.

Abstract

Individual Kekule valence structures of biphenylene and related hydrocarbons are comparatively studied in respect of their total pi-electron energies and thereby relative stabilities. These structures are modeled as sets of weakly-interacting initially-double (C=C) bonds. The relevant total energies are represented in the form of power series, wherein the averaged resonance parameter of initially-single (C-C) bonds underlies the expansion. To rationalize the resulting distinctions in total energies, interrelations are sought between separate members of the series, on the one hand, and presence of definite substructures in the given Kekule valence structure, on the other hand. It is shown that monocycles S_1 and S_2 correspondingly containing two and four exocyclic methylene groups (like 3,4-dimethylene cyclobutene and [4]radialene) participate in the formation of energy corrections of the relevant Kekule valence structures along with the usual conjugated circuits of the 4n+2 and 4n series (R_n and Q_n, n=1,2,3...). Thus, the cycles S_1 and S_2 are deductively predicted to play the role of supplementary conjugated circuits for biphenylene-like hydrocarbons. Moreover, the S_2- and S_1- containing structures are shown to be the most stable ones among all Kekule valence structures of the given hydrocarbon. Meanwhile, the lowest stability is predicted for structures in which either the neighboring hexagonal rings are connected by two C=C bonds or two exocyclic C=C bonds are attached to the same hexagonal ring.