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两种新型乙酸根-EMIM锰离子链状离子化合物的合成、表征及晶体结构,其中锰离子仅由乙酸根配位

Synthesis, Characterization, and Crystal Structures of Two New Manganese Aceto EMIM Ionic Compounds with Chains of Mn Ions Coordinated Exclusively by Acetate.

作者信息

Dera Przemyslaw, Bruffey Edward, Finkelstein Gregory J, Kelly Colleen, Gigante Angelina, Hagemann Hans, Severa Godwin

机构信息

Hawai'i Institute of Geophysics and Planetology, University of Hawai'i at Ma̅noa, 1680 East West Rd, POST 109, Honolulu, Hawai'i 96822, United States.

Hawai'i Natural Energy Institute, University of Hawai'i at Ma̅noa, 1680 East West Rd, POST 109, Honolulu, Hawai'i 96822, United States.

出版信息

ACS Omega. 2020 Jun 18;5(25):15592-15600. doi: 10.1021/acsomega.0c01820. eCollection 2020 Jun 30.

Abstract

We synthesized and determined crystal structures of two manganese(II) aceto EMIM coordination compounds with simplified empirical formulas Mn(OAc)[EMIM] and Mn(OAc)[EMIM]·2HO. Both compounds feature extended chains of Mn octahedrally coordinated exclusively by acetate anions, which has been observed for the first time. The EMIM moieties and water molecules participate in hydrogen bonding with acetate anions but do not directly interact with the metal cation. Both compounds have melting temperatures around 120 °C and can be considered as (non-room-temperature) ionic liquids. The structural arrangement represented by the two title compounds is robust in terms of accommodating other types of cations and allows for tuning of physical properties of the ionic liquid by means of cation substitution. Thermal analysis results obtained using TGA-DSC and VT IR suggest melting phase transitions around 120 °C, followed by structural rearrangement in the molten state taking place around 140-160 °C. Compounds and have a higher thermal stability range compared to [EMIM][OAc] ionic liquid, with an onset decomposition temperature above 260 °C.

摘要

我们合成并确定了两种具有简化经验式Mn(OAc)[EMIM]和Mn(OAc)[EMIM]·2H₂O的锰(II)乙酰基EMIM配位化合物的晶体结构。两种化合物均具有仅由醋酸根阴离子八面体配位的锰的延伸链,这是首次观察到的情况。EMIM部分和水分子与醋酸根阴离子参与氢键作用,但不直接与金属阳离子相互作用。两种化合物的熔点均在120°C左右,可被视为(非室温)离子液体。由这两种标题化合物所代表的结构排列在容纳其他类型阳离子方面很稳定,并允许通过阳离子取代来调节离子液体的物理性质。使用TGA-DSC和变温红外光谱获得的热分析结果表明,在120°C左右发生熔融相变,随后在140 - 160°C左右的熔融状态下发生结构重排。与[EMIM][OAc]离子液体相比,化合物1和2具有更高的热稳定性范围,起始分解温度高于260°C。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/67ad/7331212/2d0ef4db1365/ao0c01820_0001.jpg

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