Quantifying reversible nitrogenous ligand binding to Co(ii) porphyrin receptors at the solution/solid interface and in solution
Literature Information
Kristen N. Johnson, K. W. Hipps, Ursula Mazur
We present a quantitative study comparing the binding of 4-methoxypyridine, MeOPy, ligand to Co(II)octaethylporphyrin, CoOEP, at the phenyloctane/HOPG interface and in toluene solution. Scanning tunneling microscopy (STM) was used to study the ligand binding to the porphyrin receptors adsorbed on graphite. Electronic spectroscopy was employed for examining this process in fluid solution. The on surface coordination reaction was completely reversible and followed a simple Langmuir adsorption isotherm. Ligand affinities (or ΔG) for the binding processes in the two different chemical environments were determined from the respective equilibrium constants. The free energy value of −13.0 ± 0.3 kJ mol−1 for the ligation reaction of MeOPy to CoOEP at the solution/HOPG interface is less negative than the ΔG for cobalt porphyrin complexed to the ligand in solution, −16.8 ± 0.2 kJ mol−1. This result indicates that the MeOPy–CoOEP complex is more stable in solution than on the surface. Additional thermodynamic values for the formation of the surface ligated species (ΔHc = −50 kJ mol−1 and ΔSc = −120 J mol−1) were extracted from temperature dependent STM measurements. Density functional computational methods were also employed to explore the energetics of both the solution and surface reactions. At high concentrations of MeOPy the monolayer was observed to be stripped from the surface. Computational results indicate that this is not because of a reduction in adsorption energy of the MeOPy–CoOEP complex. Nearest neighbor analysis of the MeOPy–CoOEP in the STM images revealed positive cooperative ligand binding behavior. Our studies bring new insights to the general principles of affinity and cooperativity in the ligand–receptor interactions at the solution/solid interface. Future applications of STM will pave the way for new strategies designing highly functional multisite receptor systems for sensing, catalysis, and pharmacological applications.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.














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