Coulombic effects in radical-cation-based high-spin polymers

Bushby, Richard J.; McGill, D. R.; Ng, Kai Mo; Taylor, N.

doi:10.1039/cc9960002641

Cited by 10 publications

(1 citation statement)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Because the anion and cation radicals of the compounds buta-1,3-diyne and buta-1,3-diene represent the smallest conceivable conjugated ionic/radical molecules, they have found application as model compounds for larger systems, like biologically important molecules such as retinal [20] and the carotene radical cation [21] and industrially interesting systems like conducting polymers [22][23][24][25]. Understanding the stability of cation or anion radicals in conjugated systems can contribute to estimating the stability of these radicals in the gas-phase, which is essential in mass spectrometry studies of polyene systems [26,27].…”

Section: Introductionmentioning

confidence: 99%

The resonance of cation and anion radicals with multiple conjugated bonds

2014

View full text Add to dashboard Cite

This work describes a computational study of the electronic structure of anion and cation radicals of some conjugated systems-buta-1,3-diyne, hexa-1,3,5-triyne, buta-1,3-diene, and hexa-1,3,5-triene. The main purpose was to investigate how the gain or loss of one electron affected the geometry and, electron and spin densities. The NBO, QTAIM, ELF, and LMO-EDA methods helped to study the electronic structure of the target compounds and their radicals. Several methods indicate an increased electronic delocalization upon ionization. The unpaired electron is preferentially localized at the terminal carbon atoms in radicals. The calculated isodesmic and homodesmotic bond separation reactions indicated that disruption of the conjugation system prompted higher energy at the radicals as compared with neutral molecules. 2 , the total interaction energy, DE total , becomes more negative, for all the anion radicals, as compared with the neutral compounds. The larger stabilizing contributions stem from the electrostatic, exchange, and polarization components, and the repulsion energy augments. These changes could be correlated with Table 5 Total interaction energy, DE total , and electrostatic, DE elstat , repulsion, DE rep , exchange, DE exc , polarization, DE pol , and dispersion, DE disp , components for fragments of all the studied species Compound DE total / Kcal mol 21 DE elstat / Kcal mol 21 DE rep / Kcal mol 21 DE exc / Kcal mol 21 DE pol / Kcal mol 21 DE disp / Kcal mol 21

show abstract