Issue 42, 2024

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

Abstract

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 M6O88+ (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 M6O8H4(O2P(H)Ph)12 (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 M6O8 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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
12 Jun 2024
Accepted
20 Sep 2024
First published
07 Oct 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 17380-17396

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

A. R. Unniram Parambil, R. Pokratath, M. J. Parammal, E. Dhaene, D. Van den Eynden, S. Balog, A. Prescimone, I. Infante, P. Shahgaldian and J. De Roo, Chem. Sci., 2024, 15, 17380 DOI: 10.1039/D4SC03859B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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