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

作者：Yuyao Li, Zhelin Ding, Qiqi Mu, Junle Ren, Qiguang Shen, Shoufeng Zhang, Li Zhang · 发表于：Dalton Transactions · 年份：2022 · DOI：10.1039/d2dt02723b · 被引用次数：3 · 研究领域：Radical Photochemical Reactions、Synthesis and characterization of novel inorganic/organometallic compounds、Organoboron and organosilicon chemistry

]), 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 structure...