Extremely long C-C bonds predicted beyond 2.0 \r{A}

TL;DR

This study investigates the properties of conjugated molecules with extremely long C-C bonds beyond 2.0 Å, analyzing their stability, electronic character, and potential for elongation, using advanced computational methods.

Contribution

It provides detailed computational analysis of ultra-long C-C bonds, challenging previous assumptions about bond length limits and diradical character.

Findings

No direct C-C bonds beyond 2.4 Å observed in models.

Extremely stretched C-C bonds around 2.2 Å are predicted with moderate BDE.

No significant diradical character found in these long bonds.

Abstract

A number of conjugated molecules are designed with extremely long single C-C bonds beyond 2.0 \r{A}. Some of the investigated molecules are based on analogs to the recently discovered molecule by Kubo et al. These bonds are analyzed by a variety of indices in addition to their equilibrium bond length including the Wiberg bond index, bond dissociation energy (BDE), and measures of diradicaloid character. All unrestricted DFT calculations indicate no diradical character supported by high-level multireference calculations. Finally, NFOD was computed through fractional orbital density (FOD) calculations and used to compare relative differences of diradicaloid character across twisted molecules without central C-C bonding and those with extremely elongated C-C bonds using a comparison with the C-C bond breaking in ethane. No example of direct C-C bonds beyond 2.4 \r{A} are seen in the computational modeling, however, extremely stretched C-C bonds in the vicinity of 2.2 \r{A} are predicted to be achievable with a BDE of 15-25 kcal/mol.