Wang Di, Yao Dan, Li Xinyu, Shi Lingli, Wang Chunyuan, Li Jie, Kong Weili, Qin Yongliang, Baumgarten Martin
School of Materials Science and Chemical Engineering, Anhui Jianzhu University, Hefei 230601, China.
Anhui Province Key Laboratory of Condensed Matter Physics at Extreme Conditions, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China.
Molecules. 2025 Apr 26;30(9):1931. doi: 10.3390/molecules30091931.
Controllable intramolecular spin-polarized flow refers to the manipulation of spin-polarized electron transport within molecules through externally applied stimuli, thereby modulating their intramolecular spin characteristics and magnetic properties. In this work, we designed and synthesized four paramagnetic molecules, PDTN-NN, PDTN-IN, PO-NN, and PO-IN, by introducing nitronyl nitroxide (NN) and iminonitroxide (IN) radicals into phenothiazine and phenoxazine frameworks. Remarkably, we successfully generated the corresponding radical-substituted radical cations (diradical cations) and controlled their spin density distributions (SDDs) through redox stimuli. UV-Vis absorption spectroscopy, cyclic voltammetry (CV), electron paramagnetic resonance (EPR), and density functional theory (DFT) were employed to confirm the formation of diradical cations during the redox processes. Furthermore, EPR spectroscopy and DFT calculations were also employed to provide clear evidence of intramolecular magnetic coupling in the diradical cations.
可控分子内自旋极化流是指通过外部施加的刺激来操纵分子内自旋极化电子传输，从而调节其分子内自旋特性和磁性。在这项工作中，我们通过将硝酰基氮氧化物（NN）和亚氨基氮氧化物（IN）自由基引入吩噻嗪和吩恶嗪骨架中，设计并合成了四种顺磁性分子，即PDTN-NN、PDTN-IN、PO-NN和PO-IN。值得注意的是，我们通过氧化还原刺激成功生成了相应的自由基取代自由基阳离子（双自由基阳离子），并控制了它们的自旋密度分布（SDD）。利用紫外-可见吸收光谱、循环伏安法（CV）、电子顺磁共振（EPR）和密度泛函理论（DFT）来确认氧化还原过程中双自由基阳离子的形成。此外，还利用EPR光谱和DFT计算为双自由基阳离子中的分子内磁耦合提供了明确证据。
