Xu Jialiang, Zhu Li, Gao Hu, Li Chenhong, Zhu Meng-Jiao, Jia Zhen-Yu, Zhu Xin-Yang, Zhao Yue, Li Shao-Chun, Wu Fan, 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, 210046, P. R. China.
National Laboratory of Solid State Microstructures, School of Physics, Collaborative Innovation Center of, Advanced Microstructures, Nanjing University, Nanjing, 210093, P. R. China.
Angew Chem Int Ed Engl. 2021 May 17;60(21):11702-11706. doi: 10.1002/anie.202016674. Epub 2021 Apr 16.
A facile method for the quantitative preparation of silver dibenzo-fused corrole Ag-1 is described. In contrast to the saddle conformation resolved by single-crystal X-ray analysis for Ag-1, it adopts an unprecedented domed geometry, with up and down orientations, when adsorbed on an Ag(111) surface. Sharp Kondo resonances near Fermi level, both at the corrole ligand and the silver center were observed by cryogenic STM, with relatively high Kondo temperature (172 K), providing evidence for a non-innocent Ag -corrole species. Further investigation validates that benzene ring fusion and molecule-substrate interactions play pivotal roles in enhancing Ag(4d(x -y ))-corrole (π) orbital interactions, thereby stabilizing the open-shell singlet Ag -corrole on Ag(111) surface. Moreover, this strategy used for constructing metal-free benzene-ring fused corrole ligand gives rise to inspiration of designing novel metal-corrole compound for multichannel molecular spintronics devices.
本文描述了一种简便的定量制备二苯并稠合卟啉银Ag-1的方法。与通过单晶X射线分析确定的Ag-1的鞍形构象不同，当吸附在Ag(111)表面时，它呈现出前所未有的圆顶几何形状，具有上下取向。通过低温扫描隧道显微镜观察到，在卟啉配体和银中心处，费米能级附近都有尖锐的近藤共振，近藤温度相对较高(172 K)，这为非单纯的Ag-卟啉物种提供了证据。进一步的研究证实，苯环稠合和分子-底物相互作用在增强Ag(4d(x -y ))-卟啉(π)轨道相互作用中起关键作用，从而稳定了Ag(111)表面的开壳单重态Ag-卟啉。此外，这种用于构建无金属苯环稠合卟啉配体的策略为设计用于多通道分子自旋电子器件的新型金属-卟啉化合物提供了灵感。
