Structural Changes during the Growth of Atomically Precise Metal Oxido Nanoclusters from Combined Pair Distribution Function and Small‐Angle X‐ray Scattering Analysis

Anker, Andy S.; Christiansen, Troels Lindahl; Weber, Martina; Schmiele, Martin; Brok, Erik; Kjær, Emil T. S.; Juhás, Pavol; Thomas, Rico; Mehring, M.; Jensen, Kirsten M. Ø.

doi:10.1002/anie.202103641

Cited by 25 publications

(29 citation statements)

References 52 publications

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“…When studying the chemistry of nucleation, we should thus not reduce the problem to an abstract monomer, but one needs to take into account the specific chemical nature of the species. This requires detailed investigation of the coordination chemistry of precursors and their exact decomposition mechanism. ,,,,− Such studies benefit greatly from X-ray based (synchrotron) techniques, e.g., small-angle X-ray scattering (SAXS), extended X-ray absorption fine structure (EXAFS) spectroscopy, and pair distribution function (PDF) analysis. ,, …”

Section: Crystallization Into Nanocrystalsmentioning

confidence: 99%

Chemical Considerations for Colloidal Nanocrystal Synthesis

Roo

2022

Chem. Mater.

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We take here the perspective of a nanochemist on the field of colloidal nanocrystals, focusing specifically on nanocrystal synthesis. Considering the three components of a colloidal synthesis, we discuss the chemistry that occurs with precursors, ligands, and solvents. Insight into the coordination chemistry and the organic chemistry of nanocrystal syntheses brings us one step closer to a retro-synthetic analysis of a nanocrystal reaction. We also reflect on different crystallization mechanisms (either under thermodynamic or kinetic control). We consider the possibility that the different models are simply describing different experimental conditions and are not fundamentally at odds with one another. However, we do critically evaluate the use of the terms monomer and burst nucleation. Finally, we discuss good chemical practices for a nanochemist, and we try to define nanocrystal purity. This perspective will hopefully inspire researchers in colloidal nanoscience to think more about chemical equations, consider reaction by-products, and come together as a field to agree on standard reporting practices for colloidal nanocrystals.

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Section: Crystallization Into Nanocrystalsmentioning

confidence: 99%

Chemical Considerations for Colloidal Nanocrystal Synthesis

Roo

2022

Chem. Mater.

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“…In our previous work, we have demonstrated that ex situ XPDF measurements are sensitive to the identity of the cluster in UiO family MOFs and can clearly distinguish between isolated Zr atoms, Zr 6 clusters, and Zr 12 clusters and have successfully been used in situ to track the size of interlinked cluster aggregates forming MOF crystallites in solvothermal UiO-66 syntheses, as well as of metal oxido nanoclusters . However, until now, no study has been able to follow both the cluster formationespecially of higher-nuclearity clustersand the coordination of the MOF framework in the same in situ reaction.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Role of Cluster Formation in UiO Family Hf Metal–Organic Frameworks with in Situ X-ray Pair Distribution Function Analysis

Firth

Gaultois

et al. 2021

J. Am. Chem. Soc.

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The structures of Zr and Hf metal−organic frameworks (MOFs) are very sensitive to small changes in synthetic conditions. One key difference affecting the structure of UiO MOF phases is the shape and nuclearity of Zr or Hf metal clusters acting as nodes in the framework; although these clusters are crucial, their evolution during MOF synthesis is not fully understood. In this paper, we explore the nature of Hf metal clusters that form in different reaction solutions, including in a mixture of DMF, formic acid, and water. We show that the choice of solvent and reaction temperature in UiO MOF syntheses determines the cluster identity and hence the MOF structure. Using in situ X-ray pair distribution function measurements, we demonstrate that the evolution of different Hf cluster species can be tracked during UiO MOF synthesis, from solution stages to the full crystalline framework, and use our understanding to propose a formation mechanism for the hcp UiO-66(Hf) MOF, in which first the metal clusters aggregate from the M 6 cluster (as in fcu UiO-66) to the hcp-characteristic M 12 double cluster and, following this, the crystalline hcp framework forms. These insights pave the way toward rationally designing syntheses of as-yet unknown MOF structures, via tuning the synthesis conditions to select different cluster species.

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“…Previously, we demonstrated that the ligand substitution starting from [Bi 22 O 26 (OSiMe 2 t Bu) 14 ] using tert -butyloxycabonyl (Boc)-protected phenylalanine (Phe) (Boc–Phe–OH) gave [Bi 22 O 26 (Boc–Phe–O) 14 ], which quickly hydrolyses to result in the formation of [Bi 38 O 45 (Boc–Phe–O) 22 (OH) 2 ] [ 26 ]. Furthermore, we showed that the substitution of nitrate anions in [Bi 38 O 45 (NO 3 ) 20 (dmso) 28 ](NO 3 ) 4 ·4dmso is possible by the reaction with sodium methacrylate to give [Bi 38 O 45 (OMc) 24 ] (OMc = Methacrylate), as proven by in situ studies [ 12 , 16 ]. The combined hydrolysis and substitution reaction starting from bismuth nitrate and sodium carboxylates usually tends to give a [Bi 38 O 45 ] cluster core, surrounded by a mixed ligand shell of nitrates and carboxylates [ 27 ].…”

Section: Introductionmentioning

confidence: 99%

“…However, it shows poor solubility in all kinds of solvents, and easily hydrolyses to give various condensation products, of different stoichiometry and nuclearity [ 13 , 14 , 15 ]. These so-called bismuth subnitrates were recently studied in order to elucidate the molecular mechanisms of the condensation that lead to the formation of bismuth oxido nitrates with up to 38 bismuth atoms, e.g., in the nanoscaled [Bi 38 O 45 (NO 3 ) 24 ], using a combined in situ small-angle X-ray scattering (SAXS) and pair distribution function (PDF) analysis approach, as well as electrospray ionization mass spectrometry (ESI-MS) [ 16 , 17 , 18 ]. The Bi 38 O 45 core seems to be the most stable one among the bismuth oxido clusters, and various molecules of this type were reported recently, including sulfonates, salicylates, nitrates, and methacrylates [ 13 , 14 , 19 , 20 , 21 , 22 , 23 , 24 ].…”

Section: Introductionmentioning

confidence: 99%

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces

et al. 2022

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Bismuth compounds are of growing interest with regard to potential applications in catalysis, medicine, and electronics, for which their environmentally benign nature is one of the key factors. One thing that currently hampers the further development of bismuth oxido-based materials, however, is the often low solubility of the precursors, which makes targeted immobilisation on substrates challenging. We present an approach towards the solubilisation of bismuth oxido clusters by introducing an amino carboxylate as a functional group. For this purpose, the bismuth oxido cluster [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (dmso = dimethyl sulfoxide) was reacted with the sodium salt of tert-butyloxycabonyl (Boc)-protected phenylalanine (L-Phe) to obtain the soluble and chiral nanocluster [Bi38O45(Boc–Phe–O)24(dmso)9]. The exchange of the nitrates by the amino carboxylates was proven by nuclear magnetic resonance, Fourier-transform infrared spectroscopy, as well as elemental analysis and X-ray photoemission spectroscopy. The solubility of the bismuth oxido cluster in a protic as well as an aprotic polar organic solvent and the growth mode of the clusters upon spin, dip, and drop coating on gold surfaces were studied by a variety of microscopy, as well as spectroscopic techniques. In all cases, the bismuth oxido clusters form crystalline agglomerations with size, height, and distribution on the substrate that can be controlled by the choice of the solvent and of the deposition method.

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Structural Changes during the Growth of Atomically Precise Metal Oxido Nanoclusters from Combined Pair Distribution Function and Small‐Angle X‐ray Scattering Analysis

Cited by 25 publications

References 52 publications

Chemical Considerations for Colloidal Nanocrystal Synthesis

Chemical Considerations for Colloidal Nanocrystal Synthesis

Exploring the Role of Cluster Formation in UiO Family Hf Metal–Organic Frameworks with in Situ X-ray Pair Distribution Function Analysis

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces

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