Manganese metal organic frame work assisted magnetic ionic liquid single crystal

IF 3.8 Q2 CHEMISTRY, PHYSICAL
Naima Sharmin, Md. Jahidul Islam
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Abstract

This research focuses on the synthesis and characterization of a Metal-Organic Framework Assisted Ionic Liquid (MOFIL) with the chemical formula of [Mn(Cy)(R)2]R·2H2O; where, Cy is cyclam- (1,4,8,11-tetraazacyclotetradecane) and R is 4-tetradecyloxy benzoate- (4-CH3(CH2)13OC6H4COO-). This novel ionic liquid crystal is synthesized in a multistep process. The first precursor compound ethyl 4-tetradecyloxy benzoate, 4-CH3(CH2)13OC6H4COOC2H5 (A) is obtained from a reaction in between the ethyl 4‑hydroxy benzoate, 4-HOC6H4COOC2H5 and 1-bromotetradecane, CH3(CH2)13Br. Precursor A is further reacted with potassium hydroxide, KOH to yield the 2nd precursor a potassium salt of ethyl 4-tetradecyloxy benzoate, 4-CH3(CH2)13OC6H4COOK (B). Then the precursor B is reacted with manganese chloride tetrahydrate, MnCl2·4H2O to synthesize the dinuclear Manganese (II) carboxylate intermediate compound, [Mn2(R)4(H2O)4] (1). Finally, the addition of cyclam to compound (1) results in the targeted mononuclear MOFIL compound with cyclam, [Mn(Cy)(R)2]R·2H2O (2). This article reports the synthetic procedure and structural elucidation of this MOFIL compound (2) along with its precursors (A and B) and intermediate (1) compound by Fourier Transform Infra-Red (FTIR) spectroscopy, Ultraviolet- Visible (UV- Vis) spectroscopy, and single crystal X-ray crystallography. In addition, the magnetic, thermal, and optical studies of the final MOFIL (2) and its dinuclear intermediate compound (1) are also presented. The dinuclear intermediate, (1) having a higher melting temperature around 150 °C and no development of optical texture as observed by Optical Polarizing Microscope (OPM) and Differential Scanning Calorimetric (DSC) data; doesn't fulfil the criteria of being a MOFIL. In contrast, the mononuclear final compound, (2) with cyclam, is crystallized in triclinic system, showing distorted octahedral N4O2 geometry around a mononuclear d4 Mn(III) centre; that is further evidenced by it's µeff value of 4.6 BM., calculated from room temperature magnetic susceptibility measurement. Compound (2) is thermally stable (Tdec, 242 °C) according to Thermogravimetric Analysis (TGA). It exhibits mesomorphism and behaves as ionic liquid with a melting temperature <110 °C as observed by OPM and DSC data.

Abstract Image

锰金属有机骨架辅助磁性离子液体单晶
本文研究了一种化学式为[Mn(Cy)(R)2]R·2H2O的金属-有机骨架辅助离子液体(MOFIL)的合成与表征;式中,Cy为环环-(1,4,8,11-四氮杂环十四烷),R为4-十四环氧基苯甲酸酯- (4- ch3 (CH2)13OC6H4COO-)。这种新型离子液晶是通过多步骤合成的。第一个前体化合物4-羟基苯甲酸乙酯4- hoc6h4cooc2h5 (A)由4-羟基苯甲酸乙酯4- hoc6h4cooc2h5与1-溴十四烷CH3(CH2)13Br反应而得。前驱体A进一步与氢氧化钾反应得到第二前驱体1 - 4-十四环氧基苯甲酸乙酯钾盐4- ch3 (CH2)13OC6H4COOK (B),然后前驱体B与四水氯化锰MnCl2·4H2O反应合成双核羧酸锰中间体[Mn2(R)4(H2O)4](1)。最后,在化合物(1)中加入环环酰胺,得到目标单核环环酰胺MOFIL化合物。[Mn(Cy)(R)2]R·2H2O(2)。本文报道了该MOFIL化合物(2)及其前体(A和B)和中间体(1)化合物的合成过程,并利用傅里叶变换红外光谱(FTIR)、紫外-可见光谱(UV- Vis)和单晶x射线晶体学对其结构进行了分析。此外,还介绍了最终MOFIL(2)及其双核中间化合物(1)的磁性、热学和光学研究。双核中间体(1)通过光学偏光显微镜(OPM)和差示扫描量热(DSC)观察,熔点在150℃左右,没有形成光学织构;不符合作为临时部队的标准。与此相反,含环环烷的单核终化合物(2)在三斜体系中结晶,在单核d4 Mn(III)中心周围呈现扭曲的八面体N4O2几何形状;其µeff值为4.6 BM,进一步证明了这一点。,由室温磁化率测量计算。根据热重分析(TGA),化合物(2)是热稳定的(Tdec, 242℃)。OPM和DSC数据显示,熔点为110℃,为中晶型,表现为离子液体。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Physics Impact
Chemical Physics Impact Materials Science-Materials Science (miscellaneous)
CiteScore
2.60
自引率
0.00%
发文量
65
审稿时长
46 days
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