Ligand Non-innocence and Single Molecular Spintronics Properties of Ag(II) Dibenzocorrole Radical on Ag(111).

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 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 the first direct spectroscopic evidence for a non-innocent Ag II -corrole •2- species. Further investigation validates that benzene ring fusion and molecule-substrate interactions play pivotal roles in enhancing Ag (4d x2-y2 )-corrole (π) orbital interactions, thereby stabilizing the open-shell singlet Ag II -corrole •2- 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 which could be applied to the research of multichannel molecular spintronics devices for data storage and logic gates.