Ligand Non‐innocence and Single Molecular Spintronic Properties of Ag^II Dibenzocorrole Radical on Ag(111)

Abstract

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 II -corroleC 2À species. Further investigation validates that benzene ring fusion and moleculesubstrate interactions play pivotal roles in enhancing Ag(4d-(x 2 Ày 2 ))-corrole (p) orbital interactions, thereby stabilizing the open-shell singlet Ag II -corroleC 2À 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.

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

“…These magnetic behaviors were reported for silver corroles where πconjugation also interacts with the 4dx2-y2 orbital of Ag(II), but the higher torsional angles in the distorted structure obstruct the ferromagnetic coupling. Consistently, a previous study reports the strong antiferromagnetic coupling of non-metalated corroles adsorbed onto Ag (111), reaching up to −2371 cm -1 [89].…”

“…Additionally, the stacked conformation has been corroborated for the corrole adsorption onto metallic surfaces such as Au (111), Ag (111), and Pt(111) [76,[87][88][89][90]. Remarkably, the noncovalent adsorption of corroles and corrolato onto Ag (111) displayed adsorption energies in the range of 2.8 -4.7 eV [88].…”

“…Besides, the increase of planarity supports the π−π stacking with graphene-based surfaces [92]. The frontier molecular spin-orbitals are affected in similar corroles adsorbed onto Au (111), Ag (111) and Cu (111) surfaces [76,88,89,93]. These changes could be observed experimentally using scanning tunneling microscopy (STM) and Kondo resonance; nevertheless, the main effects are linked to magnetic properties.…”

Highly Stable Neutral Corrole Radical: Amphoteric Aromatic–Antiaromatic Switching and Efficient Photothermal Conversion

“…Corrole is a porphyrin analog with one less carbon and well-known as a noninnocent ligand during coordination with certain metals, generating ligand-based π-radicals . The newly prepared nickel benzocorrole radical exhibits several intriguing properties: (i) the central nickel atom balances the charge of the ligand radical, resulting in an overall neutral molecule, without a counterion or axis ligands; (ii) the central nickel atom exhibits a closed-shell d 8 electron configuration, whereas most metal-coordinated corrole radicals possess unpaired electrons at the central metal (e.g., Cu, Fe, Co, and Ag), − complicating their optical and magnetic properties with strong metal–ligand interactions; (iii) the benzo-fusion of the molecule yields an unusual a 1u -type radical. Most of the spin population (95%) is delocalized around the inner carbons, which are well protected by the peripheral substituents.…”

Ligand Non‐innocence and Single Molecular Spintronic Properties of AgII Dibenzocorrole Radical on Ag(111)

“…Top (up) and side (bottom) views of the X-ray crystal structures of 1 (a, b) and Ag-1 (c, d) are shown with thermal ellipsoids at 50 % probability. [22] Supporting Information. The Ag-2 precursor was thermally sublimed onto an Ag(111) substrate in an ultra-high vacuum (base pressure of 1 10 À10 mbar).…”