Atomically precise surface chemistry of zirconium and hafnium metal oxo clusters beyond carboxylate ligands

• Published in: Chemical science (Cambridge) Vol. 15; no. 42; pp. 17380 - 17396
• Main Authors: Unniram Parambil, Ajmal Roshan, Pokratath, Rohan, Parammal, Muhammed Jibin, Dhaene, Evert, Van den Eynden, Dietger, Balog, Sandor, Prescimone, Alessandro, Infante, Ivan, Shahgaldian, Patrick, De Roo, Jonathan
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 07-10-2024; The Royal Society of Chemistry
• Subjects: Adsorbates; Affinity; Binding; Carboxylates; Chemistry; Clusters; Crystal structure; Distribution functions; Function analysis; Hafnium; Ligands; Metal-organic frameworks; Metallic glasses; Phosphonates; Phosphonic acids; Surface chemistry
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d4sc03859b

The effectiveness of nanocrystals in many applications depends on their surface chemistry. Here, we leverage the atomically precise nature of zirconium and hafnium oxo clusters to gain fundamental insight into the thermodynamics of ligand binding. Through a combination of theoretical calculations and experimental spectroscopic techniques, we determine the interaction between the M
O
(M = Zr, Hf) cluster surface and various ligands: carboxylates, phosphonates, dialkylphosphinates, and monosubstituted phosphinates. We refute the common assumption that the adsorption energy of an adsorbate remains unaffected by the surrounding adsorbates. For example, dialkylphosphinic acids are too sterically hindered to yield complete ligand exchange, even though a single dialkylphosphinate has a high binding affinity. Monoalkyl or monoaryl phosphinic acids do replace carboxylates quantitatively and we obtained the crystal structure of M
O
H
(O
P(H)Ph)
(M = Zr, Hf), giving insight into the binding mode of monosubstituted phosphinates. Phosphonic acids cause a partial structural reorganization of the metal oxo cluster into amorphous metal phosphonate as indicated by pair distribution function analysis. These results rationalize the absence of phosphonate-capped M
O
clusters and the challenge in preparing Zr phosphonate metal-organic frameworks. We thus further reinforce the notion that monoalkylphosphinates are carboxylate mimics with superior binding affinity.