Morgenstern Annika, Thomas Rico, Sharma Apoorva, Weber Marcus, Selyshchev Oleksandr, Milekhin Ilya, Dentel Doreen, Gemming Sibylle, Tegenkamp Christoph, Zahn Dietrich R T, Mehring Michael, Salvan Georgeta
Semiconductor Physics, Institute of Physics, Chemnitz University of Technology, 09107 Chemnitz, Germany.
Coordination Chemistry, Institute of Chemistry, Chemnitz University of Technology, 09107 Chemnitz, Germany.
Nanomaterials (Basel). 2022 May 26;12(11):1815. doi: 10.3390/nano12111815.
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 BiO(NO)(dmso)·4dmso (dmso = dimethyl sulfoxide) was reacted with the sodium salt of -butyloxycabonyl (Boc)-protected phenylalanine (L-Phe) to obtain the soluble and chiral nanocluster [BiO(Boc-Phe-O)(dmso)]. 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.
铋化合物在催化、医学和电子学等潜在应用方面越来越受到关注，其环境友好性是关键因素之一。然而，目前阻碍氧化铋基材料进一步发展的一个问题是前驱体的溶解度通常较低，这使得在基底上进行有针对性的固定具有挑战性。我们提出了一种通过引入氨基羧酸盐作为官能团来溶解氧化铋簇的方法。为此，使氧化铋簇BiO(NO)(dmso)·4dmso（dmso = 二甲基亚砜）与叔丁氧羰基（Boc）保护的苯丙氨酸（L-Phe）的钠盐反应，得到可溶性手性纳米簇[BiO(Boc-Phe-O)(dmso)]。通过核磁共振、傅里叶变换红外光谱以及元素分析和X射线光电子能谱证实了硝酸盐被氨基羧酸盐取代。通过各种显微镜和光谱技术研究了氧化铋簇在质子性和非质子性极性有机溶剂中的溶解度以及在金表面进行旋涂、浸涂和滴涂时簇的生长模式。在所有情况下，氧化铋簇在基底上形成具有尺寸、高度和分布的结晶团聚体，这些可以通过溶剂和沉积方法的选择来控制。
