Quantum chemical investigation of excited state aromaticity and antiaromaticity effects in organic molecules

NAISS 2023/5-335


NAISS Medium Compute

Principal Investigator:

Henrik Ottosson


Uppsala universitet

Start Date:


End Date:


Primary Classification:

10405: Organic Chemistry

Secondary Classification:

10407: Theoretical Chemistry

Tertiary Classification:

10402: Physical Chemistry



The project is directed towards aromaticity effects in electronically excited states where my research group is internationally leading. We apply quantum chemical calculations using DFT and electron correlated wavefunction methods (CASSCF, CASPT2, DLPNO-UCCSD(T) and EOM-CC). The calculations link to on-going experimental studies in the group. The topic is based on Baird's rule which tells that species with 4n pi-electrons are aromatic and those with 4n+2 pi-electrons are antiaromatic in the lowest pipi* triplet and singlet states. A series of processes and properties can be examined and rationalized in terms of excited state aromaticity or antiaromaticity. In the next 12 months we will perform quantum chemical computations along four directions; (1) explore fundamental aspects of the excited state aromaticity and antiaromaticity concepts, (2) design molecules for photovoltaics and photoacid catalysis, (3) explore photoreactivity, particularly photodegradation of pharmaceuticals and agrochemicals, and (4) develop photoreactions for oligomerizations of volatile alkenes into biofuels. Direction 1: We will explore limitations and complications of the excited state aromaticity and antiaromaticity concepts. Recently, the concepts have been applied by a growing number of research groups internationally, but not all studies are correct. There is a need to critically examine claims of excited state Baird-aromaticity and antiaromaticity, and to unravel the limitations, complications and pitfalls. More research is especially needed on excited state aromaticity and antiaromaticity in singlet excited states. Direction 2: We earlier published two papers on computational design of chromophores for singlet fission (SF) photovoltaics. In one paper we utilized a combination of ground state Hückel aromaticity and excited state Baird aromaticity for such design (JACS 2020, 142, 5602), while in the other paper we revealed that Cibalackrot-type chromophores are Hückel-aromatic in their lowest triplet state (Chem. Sci. 2021, 12, 6159). This direction has expanded with one postdoc and one PhD student, where they especially will explore and design new SF chromophores which utilize the Baird-aromaticity concept. Direction 3: Molecules which are aromatic and stable in the electronic ground state often become antiaromatic when excited. This excited state antiaromaticity triggers photorearrangements or other photoreactions as we revealed for benzene (JACS 2020, 142, 10942). We will now explore how this impact on the photoreactivity of substituted benzenes and heteroaromatics. The majority of all pharmaceuticals and agrochemicals contain ground state aromatic parts which can photodegrade, and we will continue along this line with focus on environmental effects. Grant applications to Formas and SSF have been submitted within this direction. Direction 4: In the final project direction we will identify photochemical routes for oligomerization of small alkenes, e.g., by design of suitable photoacid catalysts where the initial screening is performed through quantum chemical calculations. Together with researchers at UNSW, Sydney, Australia, we have designed a new photosuperacid, yet, need to get it more soluble under aliphatic conditions as the present photoacid (HDMAPAN) is an extensively pi-conjugated compound. We will first explore computationally various smaller (saturated) scaffolds before going over to experimental work.