Insight into Understanding Dielectric Behavior of a Zn-MOF Using Variable-Temperature Crystal Structures, Electrical Conductance, and Solid-State 13C NMR Spectra.
Inorg Chem
; 55(22): 11716-11726, 2016 Nov 21.
Article
em En
| MEDLINE
| ID: mdl-27791361
ABSTRACT
A Zn-based metal-organic framework (MOF)/porous coordination polymer (PCP), (EMIM)[Zn(SIP)] (1) (SIP3- = 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 SIP3- serves as a µ2-bridge ligand to link two Zn2+ ions and form the dinuclear SBU, and such SBUs are connected by SIP3- 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.
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Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2016
Tipo de documento:
Article