Journal Article

PUBDB-2025-00134

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Atomically precise surface chemistry of zirconium and hafnium metal oxo clusters beyond carboxylate ligands

Unniram Parambil, A. R. (First author)Extern* ; Pokratath, R.Extern* ; Parammal, M. J.Extern* ; Dhaene, E. ; Van den Eynden, D.Extern* ; Balog, S. ; Prescimone, A. ; Infante, I. ; Shahgaldian, P. ; De Roo, J. (Corresponding author)Extern*

2024
RSC Cambridge

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Please use a persistent id in citations: doi:10.1039/D4SC03859B  doi:10.3204/PUBDB-2025-00134

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.

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Contributing Institute(s):

1. FS DOOR-User (FS DOOR-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. UNICORN - Hybrid Nanocomposite Scintillators for Transformational Breakthroughs in Radiation Detection and Neutrino Research (101098649) (101098649)
3. FS-Proposal: I-20231114 EC (I-20231114-EC) (I-20231114-EC)

Experiment(s):

1. PETRA Beamline P21.1 (PETRA III)

Appears in the scientific report 2024

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Database coverage:
; ; ; ; Chemical Reactions ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; DOAJ Seal ; Essential Science Indicators ; IF >= 5 ; Index Chemicus ; JCR ; National-Konsortium ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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