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

The effectiveness of nanocrystals in many applications greatly 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 multifaceted interaction between the [M6O8]8+ (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. We find that dialkylphosphinic acids are too sterically hindered to yield complete ligand exchange, even though a single dialkylphosphinate has similar binding affinity to a phosphonate. On the other hand, monoalkyl or monoaryl phosphinic acids replace carboxylates quantitatively and we obtained the crystal structure of M6O8H4(O2P(H)Ph)12 (M = Zr, Hf), giving a unique insight into the exact binding mode of monoalkylphosphinate. Finally, 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 M6O8 clusters and the challenge in preparing Zr phosphonate metal-organic frameworks. We further reinforce the notion that monoalkylphosphinates are carboxylate mimics with superior binding affinity.