Wu Fan, Liu Jie, Mishra Puneet, Komeda Tadahiro, Mack John, Chang Yi, Kobayashi Nagao, Shen Zhen
State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
Institute of Multidisciplinary Research for Advanced Materials (IMRAM, Tagen), Tohoku University, 2-1-1, Katahira, Aoba-Ku, Sendai 980-0877, Japan.
Nat Commun. 2015 Jun 26;6:7547. doi: 10.1038/ncomms8547.
The ability to modulate the spin states of adsorbed molecules is in high demand for molecular spintronics applications. Here, we demonstrate that the spin state of a corrole complex can be tuned by expanding its fused ring as a result of the modification to the d-π interaction between the metal and ligand. A bicyclo[2.2.2]octadiene-fused copper corrole can readily be converted into a tetrabenzocorrole radical on an Au(111) substrate during the sublimation process. In the scanning tunnelling spectroscopy spectrum, a sharp Kondo resonance appears near the Fermi level on the corrole ligand of the tetrabenzocorrole molecule. In contrast, a non-fused-ring-expanded copper corrole molecule, copper 5,10,15-triphenylcorrole, shows no such Kondo feature. Mapping of the Kondo resonance demonstrates that the spin distribution of the tetrabenzocorrole molecule can be further modified by the rotation of the meso-aryl groups, in a manner that could lead to applications in molecular spintronics.
对于分子自旋电子学应用而言，调控吸附分子自旋态的能力有着很高的需求。在此，我们证明，通过扩展其稠环，由于金属与配体之间d-π相互作用的改变，卟吩配合物的自旋态能够得到调节。在升华过程中，一种双环[2.2.2]辛二烯稠合的铜卟吩能够在Au(111)衬底上轻易地转变为四苯并卟吩自由基。在扫描隧道光谱谱图中，在四苯并卟吩分子的卟吩配体上，费米能级附近出现了一个尖锐的近藤共振。相比之下，一种未进行稠环扩展的铜卟吩分子，即5,10,15-三苯基铜卟吩，并未显示出此类近藤特征。近藤共振的映射表明，四苯并卟吩分子的自旋分布能够通过中位芳基基团的旋转进一步得到修饰，这种方式可能会在分子自旋电子学中得到应用。
