Deposition of nanosized amino acid functionalized bismuth oxido clusters on gold surfaces

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. The most common starting material is bismuth nitrate, which easily hydrolyses to give a large number of con...

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Bibliographic Details
Published inarXiv.org
Main Authors Morgenstern, Annika, Rico, Thomas, Sharma, Apoorva, Weber, Marcus, Selyshchev, Oleksandr, Milekhin, Ilya, Dentel, Doreen, Gemming, Sibylle, Tegenkamp, Christoph, Zahn, Dietrich R T, Mehring, Michael, Salvan, Georgeta
Format Paper
LanguageEnglish
Published Ithaca Cornell University Library, arXiv.org 22.03.2022
Subjects
Amino acids
Atomic force microscopy
Bismuth compounds
Carboxylates
Chemical analysis
Clusters
Condensates
Deposition
Dimethyl sulfoxide
Ethanol
Functional groups
Gold
Immersion coating
Nanoclusters
Nitrates
NMR
Nuclear magnetic resonance
Optical microscopy
Phenylalanine
Photon correlation spectroscopy
Sodium salts
Solubility
Solubilization
Solvents
Substrates
X ray photoelectron spectroscopy
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Summary: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. The most common starting material is bismuth nitrate, which easily hydrolyses to give a large number of condensation products. The so-called bismuth subnitrates are composed of bismuth oxido clusters of varying composition and nuclearity. One reason that hampers the further development of bismuth oxido-based materials, however is the low solubility of the subnitrates, which makes targeted immobilisation on substrates challenging. We present an approach towards solubilisation of bismuth oxido clusters by introducing an amino carboxylate as functional group and a study of the growth mode of these atom-precise nanoclusters on gold surfaces. 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 (Phe) to give the soluble and chiral nanocluster [Bi38O45(Boc-Phe)24(dmso)9]. The hydrodynamic diameter of the cluster was estimated with (1.4-1.6) nm (in CH3CN) and (2.2 nm-2.9) nm (in Ethanol) based on dynamic light scattering (DLS). The full exchange of the nitrates by the amino carboxylates was proven by NMR and FTIR as well as elemental analysis (EA) and XPS. 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 on Au upon spin-, dip-, and drop-coating on gold surfaces were studied. Successful deposition of bismuth oxido cluster was proven by powder XRD, FTIR, and XPS while the microstructure of the resulting films was investigated as a function of the deposition method and the solvent used by SEM, AFM, and optical microscopy.
ISSN:2331-8422