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Bismuth compounds are of growing interest with regard to potentialapplications in catalysis, medicine and electronics, for which theirenvironmentally benign nature is one of the key factors. The most commonstarting material is bismuth nitrate, which easily hydrolyses to give a largenumber of condensation products. The so-called bismuth subnitrates are composedof bismuth oxido clusters of varying composition and nuclearity. One reasonthat hampers the further development of bismuth oxido-based materials, howeveris the low solubility of the subnitrates, which makes targeted immobilisationon substrates challenging. We present an approach towards solubilisation ofbismuth oxido clusters by introducing an amino carboxylate as functional groupand a study of the growth mode of these atom-precise nanoclusters on goldsurfaces. For this purpose the bismuth oxido cluster[Bi38O45(NO3)20(dmso)28](NO3)4*4dmso (dmso=dimethyl sulfoxide) was reacted withthe sodium salt of tert-butyloxycabonyl(Boc)-protected phenylalanine (Phe) togive the soluble and chiral nanocluster [Bi38O45(Boc-Phe)24(dmso)9]. Thehydrodynamic 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). Thefull exchange of the nitrates by the amino carboxylates was proven by NMR andFTIR as well as elemental analysis (EA) and XPS. The solubility of the bismuthoxido cluster in a protic as well as an aprotic polar organic solvent and thegrowth mode of the clusters on Au upon spin-, dip-, and drop-coating on goldsurfaces were studied. Successful deposition of bismuth oxido cluster wasproven by powder XRD, FTIR, and XPS while the microstructure of the resultingfilms was investigated as a function of the deposition method and the solventused by SEM, AFM, and optical microscopy.

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