Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw, Poland.
Department of Chemistry, Faculty of Natural Sciences, University of SS Cyril and Methodius, 91701 Trnava, Slovakia.
Dalton Trans. 2019 Nov 28;48(44):16650-16660. doi: 10.1039/c9dt03553b. Epub 2019 Oct 30.
Herein, we have synthesised and characterised a novel organic-inorganic hybrid crystal, [CHNH]KCr(CN) (MACr). Thermal analysis (DSC, TGA-DTA) indicates one structural phase transition (PT) at 450 K. The modified equation of the tolerance factor, t, was used to estimate the theoretical PT temperature for a crystal with Mn(iii). According to the X-ray diffraction experiment, in the low-temperature (LT) phase, the solid-to-solid PT is described by the monoclinic space group C2/c. The creation of the ferroelastic domain structure in phase II was proved on the basis of the observation under a polarising microscope. The crystals of MACr and its isomorphous analogues with Fe(iii) and Co(iii) appeared to be semiconducting materials in the LT phase. The type of PT is order-disorder and occurs between "low" (ordered-frozen) and "high" (orientationally disordered) dielectric states. Dielectric spectroscopy was used to characterise the switching properties of the dipole moments in the vicinity of the PTs. The magnetic properties of the MACr hybrid were investigated in DC and AC modes. The DC data show a sizeable weak exchange interaction between the nearest Cr(iii) centres in the crystal lattice. The AC susceptibility data confirm a slow magnetic relaxation in the applied DC field with two relaxation channels. The low-frequency relaxation time is very long as τ = 1.4(1) s at T = 2.0 K. The organic-inorganic hybrid, described above, can be considered a rare example of multifunctional materials which exhibit dielectric, magnetic, and conductive activities.
在此,我们合成并表征了一种新型的有机-无机杂化晶体[CHNH]KCr(CN)(MACr)。热分析(DSC、TGA-DTA)表明在 450K 处存在一个结构相变(PT)。采用修正后的容忍因子 t 方程估算具有 Mn(iii)的晶体的理论 PT 温度。根据 X 射线衍射实验,在低温(LT)相,固-固 PT 由单斜空间群 C2/c 描述。在偏光显微镜下观察到相 II 中存在铁弹畴结构的形成。基于观察结果,MACr 及其与 Fe(iii)和 Co(iii)的同构类似物的晶体在 LT 相中表现为半导体材料。PT 是有序-无序型,发生在“低”(有序冻结)和“高”(取向无序)介电态之间。介电光谱用于研究介电常数附近的偶极矩的开关特性。在直流和交流模式下研究了 MACr 杂化的磁性能。直流数据显示在晶体格子中最近的 Cr(iii)中心之间存在相当大的弱交换相互作用。交流磁化率数据证实了在施加的直流场中存在两个弛豫通道的缓慢磁弛豫。低频弛豫时间非常长,在 T = 2.0K 时 τ = 1.4(1)s。上述有机-无机杂化可以被认为是具有介电、磁性和导电性的多功能材料的罕见实例。