Role of the Supporting Surface in the Thermodynamics and Cooperativity of Axial Ligand Binding to Metalloporphyrins at Interfaces

Metalloporphyrins have been shown to bind axial ligands in a variety of environments, including the vacuum/solid and solution/solid interfaces. Understanding the dynamics of such interactions is a desideratum for the design and implementation of next generation molecular devices which draw inspiration from biological systems to accomplish diverse tasks such as molecular sensing, electron transport, and catalysis to name a few. In this article, we review the current literature of axial ligand coordination to surface-supported porphyrin receptors. We will focus on the coordination process as monitored by scanning tunneling microscopy (STM) that can yield qualitative and quantitative information on the dynamics and binding affinity at the single molecule level. In particular, we will address the role of the substrate and intermolecular interactions in influencing cooperative effects (positive or negative) in the binding affinity of adjacent molecules based on experimental evidence and theoretical calculations.