Departamento de Mineralogía y Petrología, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), Apdo. 644, 48080 Bilbao, Spain.
Dalton Trans. 2013 Sep 14;42(34):12481-94. doi: 10.1039/c3dt51224j. Epub 2013 Jul 18.
M2(SeO3)F2 (M = Zn (1), Mn (2)) stoichiometric phases together with the Zn2-xMnx(SeO3)F2 compound doped at various concentrations (x = 0.002-0.2) were synthesized by employing mild hydrothermal conditions. These compounds have been characterized by scanning electron microscopy (SEM), Rietveld refinement of the X-ray powder diffraction patterns, ICP-Q-MS, thermogravimetric and thermodiffractometric analyses, and IR, UV/vis and electron paramagnetic resonance (EPR) spectroscopies. Compounds 1 and 2 crystallize in the orthorhombic Pnma space group with lattice parameters: a = 7.27903(4), b = 10.05232(6) and c = 5.26954(3) Å for the zinc species and a = 7.50848(9), b = 10.3501(12) and c = 5.47697(6) Å for the manganese phase, with Z = 4. The crystal structures of these compounds are isotypic and are built up from a 3D framework constructed by (010) sheets of [MO3F3] octahedra linked up by [SeO3] building units. Luminescence measurements of Mn2(SeO3)F2 were performed at different temperatures between 10 and 150 K. At 10 K, the emission spectrum consists of a broad band peaked at around 660 nm related to the (4)T1g→(6)A1g transition in octahedrically coordinated Mn(2+). Moreover, the influence of temperatures up to 295 K and the Mn concentration on the luminescent properties of the Zn2-xMnx(SeO3)F2 system were systematically studied. Magnetic measurements of 2 show antiferromagnetic coupling as the major interactions exhibiting a spin canting at low temperature.
M2(SeO3)F2(M=Zn(1),Mn(2))化学计量相以及不同浓度(x=0.002-0.2)掺杂的 Zn2-xMnx(SeO3)F2 化合物是通过采用温和的水热条件合成的。这些化合物通过扫描电子显微镜(SEM)、X 射线粉末衍射图谱的 Rietveld 精修、电感耦合等离子体质谱(ICP-Q-MS)、热重和热差分析以及红外(IR)、紫外/可见(UV/vis)和电子顺磁共振(EPR)光谱进行了表征。化合物 1 和 2 分别在正交晶系 Pnma 空间群中结晶,晶格参数为:锌物种的 a = 7.27903(4),b = 10.05232(6),c = 5.26954(3) Å,锰相的 a = 7.50848(9),b = 10.3501(12),c = 5.47697(6) Å,Z = 4。这些化合物的晶体结构是同型的,由通过 [SeO3] 构建单元连接的 (010) 片构建的 3D 框架组成。在 10 至 150 K 之间的不同温度下对 Mn2(SeO3)F2 进行了荧光测量。在 10 K 时,发射光谱由一个宽的带组成,峰值约为 660 nm,与八面体配位的 Mn(2+)的 (4)T1g→(6)A1g 跃迁有关。此外,还系统研究了温度高达 295 K 和 Mn 浓度对 Zn2-xMnx(SeO3)F2 系统发光性能的影响。2 的磁测量显示反铁磁耦合是主要相互作用,在低温下表现出自旋倾斜。