Theoretical investigations on P-stabilized boryl cation radicals: from the Aufbau principle to SOMO–HOMO conversion

Abstract

We report the characterization of a series of novel phosphinidene-stabilized (P-stabilized) boryl cation radicals, in which the phosphinidene and boryl are stabilised by ^iPrNHC (^iPrNHC[:C{N(iPr)C(H)}₂]), and the P-stabilized boryl (P → B) moieties are linked by 1,8-naphthalene (1PB-a), 1,10-biphenyl (1PB-b), 1,2-perylene (1PB-c), and 4,5-perylene (1PB-d), to form a series of 1PB compounds. The 2PB series is designed by adding another P-stabilized boryl (P → B) unit into the 1PB series, in which the two P-stabilized boryl (P → B) moieties for each 2PB compound are linked by 1,4,5,8-naphthalene, (2PB-a), 1,5,6,10-biphenyl (2PB-b), 1,2,7,8-perylene (2PB-c), and 4,5,10,11-perylene (2PB-d), respectively. Theoretical calculations demonstrate that for all the studied molecules, the spin density mainly locates on the B atoms. Interestingly, the series of 2PB(a–d) compounds possess SOMO–HOMO conversion properties, while 1PB(a–d) compounds obey the Aufbau principle, resulting from the difference in the number of the P-stabilized boryl (P → B) moieties and an increase of the π-conjugation bridge that lead to the significantly increased HOMO energy in 2PB(a–d) compounds, which should be responsible for the different structural properties of compounds 1PB(a–d) and 2PB(a–d). The natural bond orbital (NBO) and atoms in molecules (AIM) analysis reveal how the interactions contribute to the covalent bond between P and B atoms. Moreover, the absorption properties show that the spectra of the 2PB(a–d) compounds are red-shifted relative to those of the corresponding 1PB(a–d) compounds in the near infrared region. We hope this work can provide new insights into tuning the electronic structures of the well-defined forms of P-stabilized boryl cation radicals and expand their potential application in organic optoelectronics.