Zethrenes are interesting polycyclic aromatic hydrocarbons (PAHs), which possess unique optoelectronic and magnetic properties because of their singlet open-shell biradicaloid character, making them promising candidates for application in organic electronics. Tuning their properties is a key task in order to develop efficient compounds for practical use by balancing the desired biradicaloid character against its chemical instability. In this work, high-level theoretical multireference methods appropriate for the correct description of polyradicaloid systems are used to develop rules for doping of zethrenes by means of nitrogen taking heptazethrene (HZ) as a benchmark example. The results of the quantum chemical calculations have been concentrated on a series of quantitative descriptors such as unpaired densities and singlet-triplet (S−T) splittings. They clearly indicate different regions in the HZ where N-doping can either lead to strong enhancement of the biradicaloid character or to strong quenching towards a closed shell state. A wide scale of varying open-shell character is accessible from the different doping positions. It is shown that the S−T splittings correlate well with the total number of unpaired electrons in the medium range of biradicaloid character. For pronounced biradical character the S−T splitting decays to about zero with a margin of ±0.15 eV. In the opposite closed-shell limit, much larger S−T splittings of up to 3 eV are computed.
- multireference methods
- polycyclic aromatic hydrocarbons
- singlet/triplet splitting
- unpaired electrons