We synthesized 16 novel red-emitting Mn(IV)-substituted phosphors of the compositions MgGeF₆ : Mn, MgPbF₆ : Mn, CaMF₆ : Mn (M=Ge, Sn, Pb, Zr, Hf), SrSnF₆ : Mn, “SrTiF₆ : Mn”, BaPbF₆ : Mn, ZnMF₆ : Mn (M=Sn, Pb, Zr, Hf), and CdMF₆ : Mn (M=Pb, Hf) using a dry-chemical fluorination process completely avoiding hydrofluoric acid. In comparison with the commonly used red-emitter K₂SiF₆ : Mn (KSF) with its emission maximum at 630.8 nm, all above Ca and Sr compounds and CdHfF₆ : Mn show a blue-shift of their emission maxima, the compound SrSnF₆ : Mn even by 4.2 nm down to 626.6 nm. The compounds were characterized by powder X-ray diffraction, IR and emission spectroscopy. We additionally present the crystal structures of the unsubstituted compounds CaZrF₆, CaHfF₆, CaPbF₆, CdZrF₆, CdHfF₆, and MgHfF₆, which all crystallize isotypic in the NaSbF₆ structure type. The compound “SrTiF₆” was characterized by powder XRD and studied with evolutionary structure prediction methods, but its crystal structure could not yet be solved.

中文翻译：

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Mn(IV)-取代金属(II)六氟金属化物(IV)：合成、晶体结构和发光特性

我们合成了 16 种新型 Mn(IV) 取代磷光体，其组成为 MgGeF ₆  : Mn、MgPbF ₆  : Mn、Ca M F ₆  : Mn（M = Ge、Sn、Pb、Zr、Hf）、SrSnF ₆  ： Mn、“SrTiF ₆  : Mn”、BaPbF ₆  : Mn、Zn M F ₆  : Mn（M = Sn、Pb、Zr、Hf）和 Cd M F ₆  : Mn（M = Pb、Hf）使用干-化学氟化工艺完全避免使用氢氟酸。与常用的红色发射器 K ₂ SiF _{6 相比} : Mn (KSF) 的最大发射波长为 630.8 nm，所有上述 Ca 和 Sr 化合物以及 CdHfF ₆  : Mn 都显示出其发射最大值的蓝移，化合物 SrSnF ₆  : Mn 甚至降低了 4.2 nm 至 626.6 nm。通过粉末X射线衍射、红外光谱和发射光谱对化合物进行表征。我们另外提出了未取代的化合物 CaZrF ₆、CaHfF ₆、CaPbF ₆、CdZrF ₆、CdHfF ₆和 MgHfF _{6 的}晶体结构，它们都以 NaSbF ₆结构类型同型结晶。化合物“SrTiF ₆”通过粉末XRD表征并用演化结构预测方法进行研究，但其晶体结构尚未得到解决。