Unexpected diradical character and large magnetic spin coupling in modified porphyrins induced by inverting pyrrole rings.

Porphyrin derivatives with inverted pyrrole rings have been experimentally synthesized, and their relevant electronic and magnetic properties have great application prospects in terms of electronic devices. In this work, we rationally design the structures and computationally investigate the electronic properties of porphine and Mg/Zn-porphyrin derivatives with two inverted pyrrole rings, i.e. the dipyrrole-inverted porphine and Mg/Zn-porphyrin analogues (1NN-2H, 2NN-2H, 1NN-Mg, 2NN-Mg, 1NN-Zn and 2NN-Zn), at the B3LYP/6-311G(d,p) level. The main structural characters of these porphyrin derivatives are that the [double bond splayed left]NH units of two pyrrole rings are inverted outwards and the porphyrin-like macrocycles are distorted from square to diamond shapes. More interestingly, these dipyrrole-inverted porphyrin derivatives present diradical characters with noticeably large antiferromagnetic spin coupling constants, i.e.-982.2/-936.3 cm for 1NN-2H/2NN-2H, -796.3/-764.2 cm for 1NN-Mg/2NN-Mg and -1044.5/-1055.2 cm for 1NN-Zn/2NN-Zn, but their monopyrrole-inverted counterparts do not. Examinations of the orbital properties featuring large occupation numbers of the lowest unoccupied natural orbitals and two singly occupied molecular orbitals that are polarized in opposite directions also confirm these findings. These porphyrin derivatives have small singlet-triplet energy gaps and small energy gaps between the highest occupied molecular orbital and lowest unoccupied molecular orbital of the closed-shell singlet states. These are conducive to the emergence of diradical character and large spin coupling constants. Furthermore, the spin-alternation analyses show that each dipyrrole-inverted porphyrin derivative has two resonant structures featuring two spin-opposite single electrons, in agreement with the observed antiferromagnetic spin couplings. This work provides novel insights into the electronic structures and properties of the porphyrin derivatives with modified structures and also provides helpful information for the rational design, synthesis and characterization of new porphyrin-based magnets.