We report synthesis of two novel mixed-valence iron(II)-iron(III) formate frameworks templated by N-ethylmethylammonium (EtMeA⁺) and 2-Hydroxyethylammonium (HEA⁺) cations. X-ray diffraction shows that these compounds crystallize in the P $\overline{3}$1c niccolite-type structures. Optical studies confirm mixed-valence character of these compounds. Magnetic investigation reveals that both N-ethylmethylammonium iron formate (EtMeAFeFe) and 2-Hydroxyethylammonium iron formate (HEAFeFe) exhibit magnetic order at 36.5 and 37.0 K, respectively. EtMeAFeFe also exhibits large negative magnetization below 31.0 K indicating that this compound is an N-type ferrimagnet. We also present Raman and IR data for both compounds. In order to help assignment of modes corresponding to the EtMeA⁺ cation, we also performed quantum chemical calculations to derive the harmonic and anharmonic vibrational wavenumbers. The performed calculations revealed that protonation should affect most strongly modes related to vibrations of the N–H bonds as well as the stretching modes of the CH₂ and CH₃ groups attached to the N atom.

我们报告了由N-乙基甲基铵（EtMeA ⁺）和2-羟乙基乙基铵（HEA ⁺）阳离子为模板的两个新型混合价铁（II）-铁（III）甲酸框架的合成。X射线衍射表明这些化合物在P中结晶 $\overline{3}$1 c烟碱型结构。光学研究证实了这些化合物的混合价特性。磁性研究表明，甲酸N-乙基甲基铵铁盐（EtMeAFeFe）和甲酸2-羟乙基铵铁盐（HEAFeFe）在36.5  K和37.0 K时均表现出磁性顺序。EtMeAFeFe在31.0  K以下也表现出较大的负磁化强度，表明该化合物是N型铁氧体。我们还提供了这两种化合物的拉曼和红外数据。为了帮助分配与EtMeA ⁺相对应的模式阳离子，我们还进行了量子化学计算，以得出谐波和非谐振动波数。进行的计算表明，质子化应该最强烈地影响与N–H键振动以及与N原子相连的CH ₂和CH ₃基团的拉伸模式有关的模式。