Ferroelectric Switchable Behavior through Fast Reversible De/adsorption of Water Spirals in a Chiral 3D Metal–Organic Framework

Dong, Xi‐Yan; Li, Bo; Ma, Binbin; Li, Shijun; Dong, Mingzhe; Zhu, Yanyan; Zang, Shuang‐Quan; Song, You; Hou, Hongwei; Mak, Thomas C. W.

doi:10.1021/ja403449k

Cited by 129 publications

(59 citation statements)

References 37 publications

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“…In a related report, Mak and co-workers observed a reversible switching of ferroelectric and paraelectric states in a 3D framework induced by solvate molecules. 66 The leakage current density of 1 resolvated (10 −4 −10 −8 A·cm −2 ) measured as a function of voltage also shows a close resemblance to that of 1, while 1 desolvated shows a much lower leakage current density of 10 −7 − 10 −10 A·cm −2 (Figure 5b). Thus, the increased leakage current density for 1, vis-a-vis 1 resolvated , in comparison with that of 1 desolvated illustrates the extrinsic effects caused by solvate molecules toward the polarization.…”

Section: Chemistry Of Materialsmentioning

confidence: 76%

Potentially Ferroelectric {Cu^IIL₂}_n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly

et al. 2015

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Ferroelectrics in metal−organic materials have attracted recent interest owing to their synthetic simplicity and tunable nature. Utilizing isomeric dipodal phosphoramide ligands, L 1 [PhPO(NH 4 Py) 2 ] and L 2 [PhPO(NH 2 Py) 2 ], two new Cu II L 2 derivatives, 1 ({[CuL 1 2 (H 2 O) 2 ]·(NO 3 ) 2 ·(H 2 O) 1.5 · (CH 3 OH)} ∞ ) and 2 ([CuL 2 2 ]·(NO 3 ) 2 ), were synthesized. Compound 1 crystallizes in a noncentrosymmetric polar space group Cc as a two-dimensional framework, and 2 is a centrosymmetric complex. Electrical hysteresis (P−E loop) measurements on 1 at room temperature gave the remnant (P r ) and saturation (P s ) polarization values of 27.96 and 21.79 μC· cm −2 , respectively, which are the highest among all of the known metal−organic ferroelectric materials. Also, the P r value obtained for 1 is comparable to that of barium titanate and higher than most of the organic, polymeric, and inorganic ferroelectric materials. The permittivity measurements on 1 and 2 result in high dielectric constant values of 186.3 and 53.24, respectively, at 1 Hz frequency at room temperature. Temperature-dependent permittivity measurement on 1 yields a dielectric anomaly peak at 40°C due to phase transition assisted by desolvation. The existence of phase transition is further confirmed by differential scanning calorimetry, powder X-ray diffraction, and polarized light microscopy. A comparison of the P−E loops of 1, 1 desolvated , and 1 resolvated suggest that gasification/release of the solvate molecules from the packing structure affects the polarization in 1. ■ INTRODUCTIONMaterials having ferroelectric, multiferroic, and magnetoelectric properties are of tremendous research interest owing to their application in high-technique devices. 1−7 Particularly ferroelectric materials, characterized by switchable electric polarization, are very attractive for their utility in nonvolatile computing devices, capacitors, micro-electromechanical systems (MEMS), semiconductor chips, field-effect transistors (FETs), telecommunication signal processing units, ultrasonic medical imaging devices, and nonlinear optical devices. 8−21 Traditionally, ceramic materials of the perovskite family, for example barium titanate (BTO) and lead zirconate titanate (PZT), are used as commercial ferroelectrics. 22−27 However, certain limitations such as high-temperature processing, higher molecular weight, and high content of toxic and expensive heavier metals, etc., triggered the search for alternate sources of ferroelectric materials. 28 In this effort, a range of new age materials, viz., polymers, organic−inorganic hybrids, small molecules, and liquid crystals, have been explored for ferroelectric and multiferroic applications. 29−50 Currently, ferroelectric behavior in metal−organic materials has widely been examined due to their simple synthesis, flexibility, and low-temperature fabrication techniques. 51,52 Moreover, the structural components of the metal−organic assemblies, namely, metal ions, coordinating ligands, counteranions, and the guest molec...

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Section: Chemistry Of Materialsmentioning

confidence: 76%

Potentially Ferroelectric {Cu^IIL₂}_n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly

et al. 2015

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“…Mak et al illustrated the role of water as a trigger by (10) (H 4 L = N-(1,3-dicarboxy-5-benzyl)carboxymethylglycine; bpe = 1,3-bis(4-pyridyl)ethene) with water molecules decorated in a helical fashion. [23] The compound loses the water molecules in two steps, thereby giving rise to dehydrated…”

Section: Kitagawa and Co-workers Have Demonstrated A Sensing Methods Fmentioning

confidence: 99%

“…Water-induced reversible structural changes in 10 (1 infigure), 11 (2 in figure), and 12 (3 infigure)with modulation in associated ferroelectric properties. Reproduced with permission from Ref [23]…”

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confidence: 99%

Stimulus‐Responsive Metal–Organic Frameworks

Nagarkar

Desai

Ghosh

2014

Chemistry An Asian Journal

114

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Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future "smart" technology materials. Metal-organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host-guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare. This review highlights the recent developments in the field of stimulus-responsive MOFs or so-called smart MOFs. In particular, the various stimuli used and the utility of stimulus-responsive smart MOFs for various applications such as gas storage and separation, sensing, clean energy, catalysis, molecular motors, and biomedical applications are highlighted by using representative examples. Future directions in the developments of stimulus-responsive smart MOFs and their applications are proposed from a personal perspective.

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“…Nowadays, chiral metal coordination polymers (CMCPs) have achieved considerable progress in material chemistry and supramolecular chemistry [1][2][3][4][5][6][7][8][9][10]. A particularly attracting area in this field is the exploration of their potential applications in nonlinear optics, sensor technology, enantioselective separation and asymmetric catalysis, which are especially important for the chemical and pharmaceutical industries [11][12][13][14][15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structures and properties of two new chiral rare earth-organic frameworks constructed by l/d-tartaric acid

Zhang

Miao

et al. 2015

Journal of Solid State Chemistry

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Ferroelectric Switchable Behavior through Fast Reversible De/adsorption of Water Spirals in a Chiral 3D Metal–Organic Framework

Cited by 129 publications

References 37 publications

Potentially Ferroelectric {Cu^IIL₂}_n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly

Potentially Ferroelectric {Cu^IIL₂}_n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly

Stimulus‐Responsive Metal–Organic Frameworks

Synthesis, structures and properties of two new chiral rare earth-organic frameworks constructed by l/d-tartaric acid

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Ferroelectric Switchable Behavior through Fast Reversible De/adsorption of Water Spirals in a Chiral 3D Metal–Organic Framework

Cited by 129 publications

References 37 publications

Potentially Ferroelectric {CuIIL2}n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly

Potentially Ferroelectric {CuIIL2}n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly

Stimulus‐Responsive Metal–Organic Frameworks

Synthesis, structures and properties of two new chiral rare earth-organic frameworks constructed by l/d-tartaric acid

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Product

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Potentially Ferroelectric {Cu^IIL₂}_n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly

Potentially Ferroelectric {Cu^IIL₂}_n Based Two-Dimensional Framework Exhibiting High Polarization and Guest-Assisted Dielectric Anomaly