Dolyniuk Juli-Anna, Kaseman Derrick C, Sen Sabyasachi, Zhao Jing, Osterloh Frank E, Kovnir Kirill
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA 95616 (USA).
Chemistry. 2014 Aug 18;20(34):10829-37. doi: 10.1002/chem.201305078. Epub 2014 May 21.
A polyphosphide, mP-BaP3, with a unique two-dimensional phosphorus layer has been discovered and characterized. It crystallizes in the monoclinic space group P2₁/c with unit-cell parameters a=6.486(1), b=7.710(1), c=8.172(2) Å; β=104.72(3)°; Z=4. Its phosphorus polyanion can be derived from the strong elongation of 2/3 of the P-P bonds present in the layers of black phosphorus. The unit-cell volume of the mP-BaP3 phase is 1.4% larger than the volume of another polymorph, mS-BaP3, reported more than 40 years ago. The latter phase features the presence of one-dimensional phosphorus chains separated by Ba atoms. The differences in the structures of the phosphorus fragments in both polymorphs of barium triphosphide result in large differences in both the thermal stability of these materials as well as in their properties as evidenced by DSC, (31)P solid-state MAS NMR, UV/Vis, and surface photovoltage spectroscopies, alongside quantum-chemical calculations.
一种具有独特二维磷层的多磷化物mP-BaP₃已被发现并表征。它以单斜空间群P2₁/c结晶，晶胞参数a = 6.486(1)、b = 7.710(1)、c = 8.172(2) Å；β = 104.72(3)°；Z = 4。其磷多阴离子可源自黑磷层中2/3的P-P键的强烈伸长。mP-BaP₃相的晶胞体积比40多年前报道的另一种多晶型物mS-BaP₃的体积大1.4%。后一相的特征是存在由Ba原子隔开的一维磷链。三钡磷两种多晶型物中磷片段结构的差异导致这些材料的热稳定性及其性质都存在很大差异，差示扫描量热法（DSC）、³¹P固体高分辨魔角旋转核磁共振（³¹P固体MAS NMR）、紫外/可见光谱以及表面光电压光谱以及量子化学计算都证明了这一点。
