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@ARTICLE{UnniramParambil:622022,
      author       = {Unniram Parambil, Ajmal Roshan and Pokratath, Rohan and
                      Parammal, Muhammed Jibin and Dhaene, Evert and Van den
                      Eynden, Dietger and Balog, Sandor and Prescimone, Alessandro
                      and Infante, Ivan and Shahgaldian, Patrick and De Roo,
                      Jonathan},
      title        = {{A}tomically precise surface chemistry of zirconium and
                      hafnium metal oxo clusters beyond carboxylate ligands},
      journal      = {Chemical science},
      volume       = {15},
      number       = {42},
      issn         = {2041-6520},
      address      = {Cambridge},
      publisher    = {RSC},
      reportid     = {PUBDB-2025-00134},
      pages        = {17380-17396},
      year         = {2024},
      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.},
      cin          = {FS DOOR-User},
      ddc          = {540},
      cid          = {$I:(DE-H253)FS_DOOR-User-20241023$},
      pnm          = {6G3 - PETRA III (DESY) (POF4-6G3) / UNICORN - Hybrid
                      Nanocomposite Scintillators for Transformational
                      Breakthroughs in Radiation Detection and Neutrino Research
                      (101098649) / FS-Proposal: I-20231114 EC (I-20231114-EC)},
      pid          = {G:(DE-HGF)POF4-6G3 / G:(EU-Grant)101098649 /
                      G:(DE-H253)I-20231114-EC},
      experiment   = {EXP:(DE-H253)P-P21.1-20150101},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:39386907},
      UT           = {WOS:001327118800001},
      doi          = {10.1039/D4SC03859B},
      url          = {https://bib-pubdb1.desy.de/record/622022},
}