Measuring Relative Energies of Ligand Binding Conformations on Nanocluster Surfaces with Temperature-Dependent FTIR Spectroscopy

• Published in: Journal of physical chemistry. C Vol. 127; no. 34; pp. 16970 - 16978
• Main Authors: Klein, Megan D., Bisted, Casey H., Dou, Florence Y., Sandwisch, Jason W., Cossairt, Brandi M., Khalil, Munira
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 31.08.2023
• Subjects: C: Spectroscopy and Dynamics of Nano, Hybrid, and Low-Dimensional Materials; Chemistry; Materials Science; Science & Technology - Other Topics
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.3c03951

We present a method to measure relative energies between binding conformations of carboxylate ligands on InP magic-sized clusters in solution. Using Markov chain Monte Carlo global fitting analysis on temperature-dependent vibrational spectra of cluster-bound ligands, we observe significantly different relative energies between various bidentate and monodentate binding motifs. Relative to the monodentate motif, the chelating conformation is 0.7 ± 0.3 kcal/mol more stable and the syn–syn bridging conformation is 1.1 ± 0.5 kcal/mol more stable, but the syn–anti bridging conformation exhibits no significant difference. Our results demonstrate that the relative energy between monodentate-bound carboxylates and unbound carboxylic acids is 4.52 ± 0.05 kcal/mol, or 1582 ± 19 cm–1, nearly identical to the carboxylate asymmetric stretching frequency. We suggest that the ligand vibrational energy may play a key role in ligand dissociation by compensating for energy differences between bound and dissociated ligand states. This approach gives important experimental insights into ligand binding and can inform future nanocrystal surface engineering.