Interactions and Self-Assembly of Stable Hydrocarbon Radicals on a Metal Support

Stable hydrocarbon radicals are able to withstand ambient conditions. Their combination with a supporting surface is a promising route toward novel functionalities or carbon-based magnetic systems. This will remain elusive until the interplay of radical–radical interactions and interface effects is fundamentally explored. We employ the tip of a low-temperature scanning tunneling microscope as a local probe in combination with density functional theory calculations to investigate with atomic precision the electronic and geometric effects of a weakly interacting metal support on an archetypal hydrocarbon radical model system, i.e., the exceptionally stable spin-1/2 radical α,γ-bisdiphenylene-β-phenylallyl (BDPA). Our study demonstrates the self-assembly of stable and regular one- and two-dimensional radical clusters on the Au(111) surface. Different types of geometric configurations are found to result from the interplay between the highly anisotropic radical–radical interactions and interface effects. We investigate the interaction mechanisms underlying the self-assembly processes and utilize the different configurations as a geometric design parameter to demonstrate energy shifts of up to 0.6 eV of the radicals’ frontier molecular orbitals responsible for their electronic, magnetic, and chemical properties

Spectroscopic Scanning Tunneling Microscopy Studies of Single Surface-Supported Free-Base Corroles

Corroles are versatile chemically active agents in solution. Expanding their applications toward surface-supported systems requires a fundamental knowledge of corrole–surface interactions. We employed the tip of a low-temperature scanning tunneling microscope as local probe to investigate at the single-molecule level the electronic and geometric properties of surface-supported free-base corrole molecules. To provide a suitable reference for other corrole-based systems on surfaces, we chose the archetypal 5,10,15-tris­(pentafluorophenyl)­corrole [H₃(TpFPC)] as model system, weakly adsorbed on two surfaces with different interaction strengths. We demonstrate the nondissociative adsorption of H₃(TpFPC) on pristine Au(111) and on an intermediate organic layer that provides sufficient electronic decoupling to investigate geometric and frontier orbital electronic properties of almost undisturbed H₃(TpFPC) molecules at the submolecular level. We identify a deviating adsorption behavior of H₃(TpFPC) compared to structurally similar porphyrins, characterized by a chiral pair of molecule–substrate configurations