Modulation of the molecular spintronic properties of adsorbed copper corroles

Abstract

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.

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

“…However, Ag‐1 appears to adopt an unprecedented “dome‐like” configuration, rather than the usual “saddle‐like” configuration determined by X‐ray crystallography. A previous report indicated that substrate‐molecule interactions can change the configuration of a molecule adsorbed on a substrate surface [5c] . In contrast to our previously reported copper tetrabenzocorrole, we observed both a protruded spot and a hollow area at the location of the central Ag atom in the STM map of Ag‐1 .…”

Iodine substituted phosphorus corrole complexes as possible photosensitizers in photodynamic therapy: Insights from theory

“…Due to their relatively easy synthetic accessibility and some peculiar properties, phosphorus (V) corrole complexes have been proposed for a series of interesting applications in the fields of catalysis, chemical sensors, triplet photosensitizers, molecular spintronics, and PDT . Recently, the triplet quantum yield of a series of Iodine substituted phosphorus corrole complexes has been experimentally detected .…”

Phosphorus corrole complexes: from property tuning to applications in photocatalysis and triplet–triplet annihilation upconversion

“…ISC enhancement was encouraged by bromides or iodides,38,39 which in the corrole case are present on the corrole skeleton and hence not released to the environment 40,41. Corroles with reasonable ISC probability have been introduced for photodynamic therapy,34,42,43 molecular spintronics,44 energy transfer studies,45 and oxygen sensing 35. But to the best of our knowledge, corroles were rarely used for TTA upconversion,32,46 despite the easy tuning of their redox and photophysical properties and the extremely high stability regarding demetallation.…”