Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco, UPV/EHU, Apdo.644, E-48080 Bilbao, Spain.
Inorg Chem. 2011 Dec 19;50(24):12463-76. doi: 10.1021/ic201226t. Epub 2011 Nov 15.
The Mn(2)(HPO(3))F(2) phase has been synthesized as single crystals by using mild hydrothermal conditions. The compound crystallizes in the orthorhombic Pnma space group, with unit cell parameters of a = 7.5607(8), b = 10.2342(7), and c = 5.5156(4) Å, with Z = 4. The crystal structure consists of a three-dimensional framework formed by alternating (010) layers of [MnO(3)F(3)] octahedra linked up by three connected [HPO(3)] tetrahedra. Luminescence measurements were performed at different temperatures between 10 and 150 K. The 10 K emission spectrum of the octahedrally coordinated Mn(II) cation exhibits a broad band centered at around 615 nm corresponding to the (4)T(1) → (6)A(1) transition. In order to explore the effect of the Mn(II) concentration and the possibility of enhancing the luminescence properties of the Mn(II) cation in Mn(2)(HPO(3))F(2), different intermediate composition members of the finite solid solution with the general formula (Mn(x)Zn(1-x))(2)(HPO(3))F(2) were prepared and their luminescent properties studied. The magnetic and specific heat behavior of M(2)(HPO(3))F(2) (M = Mn, Fe) have also been investigated. The compounds exhibit a global antiferromagnetic ordering with a spin canting phenomenon detected at approximately 30 K. The specific heat measurements show sharp λ-type peaks at 29.7 and 33.5 K for manganese and iron compounds, respectively. The total magnetic entropy is consistent with spin S = 5/2 and S = 2 of Mn(II) and Fe(II) cations.
已经通过使用温和的水热条件合成了 Mn(2)(HPO(3))F(2) 单晶体。该化合物在正交 Pnma 空间群中结晶,具有 a = 7.5607(8)、b = 10.2342(7)和 c = 5.5156(4)Å 的单位晶胞参数,Z = 4。晶体结构由通过三个相连的[HPO(3)]四面体连接的交替(010)层[MnO(3)F(3)]八面体组成的三维框架组成。在 10 至 150 K 的不同温度下进行了发光测量。八面体配位的 Mn(II)阳离子的 10 K 发射光谱显示出一个中心在 615nm 左右的宽带,对应于(4)T(1)→(6)A(1)跃迁。为了探索 Mn(II)浓度的影响以及在 Mn(2)(HPO(3))F(2)中增强 Mn(II)阳离子发光性能的可能性,制备了具有通式(Mn(x)Zn(1-x))(2)(HPO(3))F(2)的有限固溶体的不同中间组成成员,并研究了它们的发光性能。还研究了 M(2)(HPO(3))F(2)(M = Mn,Fe)的磁性和比热行为。这些化合物表现出全局反铁磁有序,在大约 30 K 时检测到自旋倾斜现象。比热测量显示锰和铁化合物分别在 29.7 和 33.5 K 处出现尖锐的λ型峰。总磁熵与 Mn(II)和 Fe(II)阳离子的自旋 S = 5/2 和 S = 2 一致。