Phys Chem Chem Phys. 2017 Oct 04;19(38):25979-25988. doi: 10.1039/c7cp05460b.

Optical and magnetic properties of antiaromatic porphyrinoids.

Physical chemistry chemical physics : PCCP

Rashid R Valiev, Heike Fliegl, Dage Sundholm

PMID: 28920596 DOI: 10.1039/c7cp05460b

Abstract

Magnetic and spectroscopic properties of a number of formally antiaromatic carbaporphyrins, carbathiaporphyrins and isophlorins with 4n π electrons have been investigated at density functional theory and ab initio levels of theory. The calculations show that the paratropic contribution to the magnetically induced ring-current strength susceptibility and the magnetic dipole-transition moment between the ground and the lowest excited state are related. The vertical excitation energy (VEE) of the first excited state decreases with increasing ring-current strength susceptibility, whereas the VEE of the studied higher-lying excited states are almost independent of the size of the ring-current strength susceptibility. Strong antiaromatic porphyrinoids, based on the magnitude of the paratropic ring-current strength susceptibility, have small energy gaps between the highest occupied and lowest unoccupied molecular orbitals and a small VEE of the first excited state. The calculations show that only the lowest S

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