Woo Katherine E, Wang Jian, Mark Justin, Kovnir Kirill
Department of Chemistry , Iowa State University , Ames , Iowa 50011 , United States.
Ames Laboratory , U.S. Department of Energy , Ames , Iowa 50011 , United States.
J Am Chem Soc. 2019 Aug 21;141(33):13017-13021. doi: 10.1021/jacs.9b06803. Epub 2019 Aug 9.
Over 20 years after the last inorganic ternary B-P compound was reported, NaBP, a new compound containing one-dimensional B-P polyanionic chains has been synthesized. Common high-temperature synthetic methods required for the direct reaction of boron and phosphorus negate the possible formation of metastable or low temperature phases. In this study, oxidative elimination was used to successfully condense 0D BP anionic monomers found in a NaBP precursor into unique 1D BP chains consisting of five-member BP rings connected by bridging P atoms in the crystal structure of NaBP. The synthesis was guided by X-ray powder diffraction studies, which revealed the metastable nature of the products of oxidative elimination reactions. NaBP is predicted to be an electron balanced semiconductor which was confirmed by UV-vis spectroscopy with the experimentally determined band gap of 1.1 eV.
在最后一种无机三元硼磷化合物被报道20多年后，一种含有一维硼磷聚阴离子链的新化合物NaBP已被合成。硼和磷直接反应所需的常见高温合成方法排除了亚稳相或低温相形成的可能性。在本研究中，采用氧化消除法成功地将NaBP前驱体中发现的零维BP阴离子单体缩合为独特的一维BP链，该链由在NaBP晶体结构中通过桥连磷原子连接的五元BP环组成。该合成过程由X射线粉末衍射研究指导，该研究揭示了氧化消除反应产物的亚稳性质。NaBP预计是一种电子平衡半导体，紫外可见光谱证实了这一点，其实验测定的带隙为1.1 eV。
