Aromaticity and Antiaromaticity Reversals between the Electronic Ground State and the Two Lowest Triplet States of Thiophene

Abstract

It is shown, by examining the variations in off-nucleus isotropic magnetic shielding around a molecule, that thiophene which is aromatic in its electronic ground state (S₀) becomes antiaromatic in its lowest triplet state (T₁) and then reverts to being aromatic in T₂. Geometry relaxation has an opposite effect on the aromaticities of the ππ* vertical T₁ and T₂: The antiaromaticity of T₁ is reduced whereas the aromaticity of T₂ is enhanced. The shielding picture around T₂ is found to closely resemble those around certain second singlet ππ* excited states (S₂), for example, those of benzene and cyclooctatetraene, thought to be "strongly aromatic" because of their very negative nucleus-independent chemical shift (NICS) values. It is argued that while NICS values correctly follow the changes in aromaticity along the potential energy surface of a single electronic state, the use of NICS values for the purpose of quantitative comparisons between the aromaticities of different electronic states cannot be justified theoretically and should be avoided. "Strongly aromatic" S₂ and T₂ states should be referred to simply as "aromatic" because detailed comparisons between the properties of these states and those of the corresponding S₀ states do not suggest higher levels of aromaticity.

Keywords: Baird's rule; Excited state aromaticity reversals; Nucleus-independent chemical shift; Off-nucleus shielding; Thiophene.

Figure 1

Atom numbering scheme for thiophene.

Figure 2

Isotropic shielding isosurfaces at σ _iso(r)=±16 ppm (“+” in blue, “−” in orange) for the S₀, T₁ and T₂ electronic states of thiophene. The T₁//S₀ and T₂//S₀ isosurfaces correspond to the S₀→T₁ and S₀→T₂ vertical excitations, respectively. For details, see text.

Figure 3

Isotropic shielding contour plots in the vertical symmetry planes passing through the sulfur atoms and the midpoints of the opposite carbon‐carbon bonds for the S₀, T₁ and T₂ electronic states of thiophene. Contour levels requested at −30(5)−5, 10(5)50, 60(20)240 ppm, orange (deshielded) to blue (shielded). Solid black lines show the projections of the carbon‐sulfur and carbon‐carbon bonds. The positions of NICS(0) and NICS(±1) are marked by crosses and connected by dashed lines.