Elementary conjugated fragments in acyclic polyenes with heteroatoms

TL;DR

This paper identifies key substructures in heteroatom-containing polyenes that influence their conjugation energy, using a model based on weakly-interacting double bonds and power series analysis.

Contribution

It introduces a novel approach to analyze conjugated fragments in heteroatom polyenes, highlighting elementary conjugated fragments that affect electronic properties.

Findings

Identified nine elementary conjugated fragments involving heteroatoms.

Demonstrated the influence of fragment structure on conjugation energy.

Provided a theoretical framework for analyzing charge redistribution in polyenes.

Abstract

The study is aimed at revealing the most important substructures (fragments) of polyenes with heteroatoms determining the alteration in the conjugation energy of the whole compound due to substitution and the relevant charge redistribution. The systems are modelled as sets of weakly-interacting formally-double bonds, where the formally-single bonds represent the interaction. Expressions for total energies and populations of basis orbitals are then derived in the form of power series with respect to two small parameters. Analysis of these series shows that conjugated substructures consisting of two connected formally-double bonds and containing at least s single heteroatom play the role of fragments being sought. Nine potential fragments of this type are considered separately that differ one from another in the number of heteroatoms and/or their relative positions inside and are called elementary conjugated fragments.