Simple but Useful Scheme toward Understanding of Intramolecular Magnetic Interactions: Benzene-Bridged Oxoverdazyl Diradicals

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• 作者：Kyoung Chul Ko ; Young Geun Park ; Daeheum Cho ; Jin Yong Lee
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：October 9, 2014
• 年：2014
• 卷：118
• 期：40
• 页码：9596-9606
• 全文大小：450K
• ISSN：1520-5215

文摘

It has recently been shown that the types of intramolecular magnetic interactions of diradical systems can be changed by the types of radical group: syn-group (or 伪-group) and anti-group (or 尾-group). The aim of this study is to establish a useful scheme to understand and explain the intramolecular magnetic interactions in diradical systems regardless of radical groups and the topology of a coupler. We investigated the intramolecular magnetic coupling constant (J) of six oxoverdazyl diradicals (i鈥?b>vi) coupled with a benzene ring based on the unrestricted DFT calculations. On the basis of our results, we devised a simple but useful scheme by combining the spin alternation rule and the concept of radical group classification. Consequently, it was found that the calculated J values and plots of spin density distributions were consistent with our proposed scheme. In addition, we discussed the closed-shell singlet (CS) state and the dihedral angle effect on J values in detail to comprehensively understand the magnetic interactions of diradical systems. Our scheme can provide the basic framework to design future organic high-spin molecules and organic magnetic materials.