publications in 2023

Carbon–carbon σ-single bonds are crucial for constructing molecules like ethane derivatives (R3C–CR3), which are composed of tetrahedral four-coordinate carbons. Molecular functions, such as light absorption or emission, originate from the π-bonds existing in ethylene derivatives (R2C═CR2). In this study, a relatively stable cyclopentane-1,3-diyl species with π-single bonding system (C−π–C) with planar four-coordinate carbons is constructed. This diradicaloid is energetically more stable than the corresponding σ-single bonding system. The π-electron single bonding system provides deeper insights into the chemical bonding and the physical properties derived from the small energy gaps between the bonding and antibonding molecular orbitals.

Unique spin–spin (magnetic) interactions, ring-size effects on ground-state spin multiplicity, and in-plane aromaticity has been found in localized 1,3-diradicals embedded in curved benzene structures such as cycloparaphenylene (CPP). In this study, we characterized the magnetic interactions in a tetraradical consisting of two localized 1,3-diradical units connected by p-quaterphenyl within a curved CPP skeleton by electron paramagnetic resonance (EPR) spectroscopy and quantum chemical calculations. Persistent triplet species with zero-field splitting parameters similar to those of a triplet 1,3-diphenylcyclopentane-1,3-diyl diradical were observed by continuous wave (CW) or pulsed X-band EPR measurements. The quintet state derived from the ferromagnetic interaction between the two triplet diradical moieties was not detected at 20 K under glassy matrix conditions. At the B3LYP/6-31G(d) level of theory, the singlet state was lower in energy than the triplet and quintet states. These findings will aid in the development of open-shell species for material science application.