Insight into Understanding Dielectric Behavior of a Zn-MOF Using Variable-Temperature Crystal Structures, Electrical Conductance, and Solid-State 13C NMR Spectra,Inorganic Chemistry

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Insight into Understanding Dielectric Behavior of a Zn-MOF Using Variable-Temperature Crystal Structures, Electrical Conductance, and Solid-State 13C NMR Spectra
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2016-10-28 00:00:00 , DOI: 10.1021/acs.inorgchem.6b01759
Yuan-Bo Tong ₁ , Shao-Xian Liu ₁ , Yang Zou ₁ , Chen Xue ₁ , Hai-Bao Duan _{1,

2} , Jian-Lan Liu ₁ , Xiao-Ming Ren _{1,

3,

4}

Affiliation

A Zn-based metal-organic framework (MOF)/porous coordination polymer (PCP), (EMIM)[Zn(SIP)] (1) (SIP^3– = 5-sulfoisophthalate, EMIM⁺ = 1-ethyl-3-methylimidazolium), was synthesized using the ionothermal reaction. The Zn²⁺ ion adopts distorted square pyramid coordination geometry with five oxygen atoms from three carboxylates and one sulfo group. One of two carboxylates in SIP^3– serves as a μ₂-bridge ligand to link two Zn²⁺ ions and form the dinuclear SBU, and such SBUs are connected by SIP^3– ligands to build the three-dimensional framework with rutile (rtl) topology. The cations from the ion-liquid fill the channels. This MOF/PCP shows two-step dielectric anomalies together with two-step dielectric relaxations; the variable-temperature single-crystal structure analyses disclosed the dielectric anomaly occurring at ca. 280 K is caused by an isostructural phase transition. Another dielectric anomaly is related to the dynamic disorder of the cations in the channels. Electric modulus, conductance, and variable-temperature solid-state ¹³C CP/MAS NMR spectra analyses revealed that two-step dielectric relaxations result from the dynamic motion of the cations as well as the direct-current conduction and electrode effect, respectively.

中文翻译：

通过变温晶体结构，电导率和固态¹³ C NMR光谱深入了解Zn-MOF的介电行为

锌基金属有机骨架（MOF）/多孔配位聚合物（PCP），（EMIM）[Zn（SIP）]（1）（SIP ^3– = 5-磺基间苯二甲酸酯，EMIM ⁺ = 1-乙基-3-甲基咪唑鎓），是利用离子热反应合成的。Zn ²⁺离子采用扭曲的方金字塔配位几何结构，具有来自三个羧酸盐和一个磺基的五个氧原子。一个在SIP 2个的羧酸盐的^3-用作μ ₂ -bridge配体与连结两个Zn ²⁺离子和形成双核SBU，并且这样的SBU通过SIP连接^-3-配体构建具有金红石的三维骨架（RTL）拓扑。来自离子液体的阳离子充满通道。此MOF / PCP显示两步介电异常以及两步介电弛豫；可变温度单晶结构分析揭示了介电异常发生在约。280 K是由同构相变引起的。另一个介电异常与通道中阳离子的动态无序有关。电模量，电导和可变温度固态¹³ C CP / MAS NMR光谱分析表明，阳离子的动态运动以及直流电传导和电极效应分别导致两步介电弛豫。

更新日期：2016-10-28

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