Reversible Phase Transition Triggered by Order–Disorder Transformation of Carboxyl Oxygen Atoms Coupled with Distinct Reorientations in [HN(C4H9)3](fumrate)0.5·(fumaric acid)0.5

Asghar, Muhammad Adnan; Sun, Zhihua; Ji, Chengmin; Zhang, Shuquan; Liu, Sijie; Li, Lina; Zhao, Sangen; Luo, Junhua

doi:10.1021/acs.cgd.5b01452

Cited by 20 publications

(12 citation statements)

References 40 publications

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“…[1][2][3][4][5][6][7][8][9][10] The architecture and design of such stimuli-responsive structural phase-transition materials (SPTMs) are not only imperative for nding multifunctional materials with novel properties but also very valuable for studying the structure-property relationships. [11][12][13][14][15] Such materials are capable of switching between two or more states, which can thus be employed for multiple purposes 16 including rewritable data storage, [17][18][19][20] memory devices, [21][22][23] switchable dielectric, magnetic and optical functionalities. 24 Generally, these physical responses undergo abrupt changes around the phase transition temperature (T c ).…”

Section: Introductionmentioning

confidence: 99%

N-Methylpyrrolidinium hydrogen tartrate (NMPHT): an above-room-temperature order–disorder molecular switchable dielectric material

et al. 2017

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A novel molecular switchable dielectric material N-methylpyrrolidinium hydrogen tartrate (NMPHT) has been synthesized, which undergoes above room temperature phase transition. Thermal measurements, e.g. differential scanning calorimetry and specific heat, confirm the presence of a phase transition around 317.5 K. The dielectric measurement displays a distinct step-like anomaly around T c , showing two different dielectric states, which reveals that NMPHT is a switchable dielectric material. The single-crystal Xray diffraction analyses at variable temperatures demonstrate that the phase transition emerges from the severe disordering of the N-methylpyrrolidinium (NMP) cation, and during the transition the symmetry of NMPHT is transformed from higher (C2/c) to lower (P2 1 /n). These findings will provide a new horizon to design smart dielectric structural phase transition materials by incorporating a flexible NMP based scaffold.

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Section: Introductionmentioning

confidence: 99%

N-Methylpyrrolidinium hydrogen tartrate (NMPHT): an above-room-temperature order–disorder molecular switchable dielectric material

et al. 2017

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“…It seems to be critical to assemble tunable and switchable materials with reorientational moieties which can display dynamical disorder in the relatively high temperature state, and turn to be ordered in the low‐temperature state. They are usually sensitive to external stimuli, thus triggering dielectric and photoluminescent phase transitions, which provides the massive possibility that dielectricity and photoluminescence could be switched between high dielectric state/low optical state and low dielectric state/high optical state upon thermal stimulus simultaneously …”

Section: Introductionmentioning

confidence: 99%

The First Molecule‐Based Blue‐Light Optical‐Dielectric Switching Material in Both Hybrid Bulk Crystal and Flexible Thin Film Forms

Guo

Zhang

et al. 2017

Advanced Optical Materials

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Three Japanese scientists are awarded the 2014 Nobel Prize in Physics for the invention of a new energy‐efficient light source, the blue light‐emitting diode, which has great potential in photoelectric applications. However, exploring excellent blue‐light materials is still a bigger challenge than red/green ones, especially those with optical‐dielectric dual channels of dielectricity and photoluminescence, which are rarely reported and gradually become the main research objects and nodi in the information industry. Herein, the first molecular blue‐light switching material, (4‐methoxybenzylaminum)2ZnCl4 (1) with many advantages, such as light weight, easy, and environment‐friendly processing, controllability, flexibility, and so on, performs optical and dielectric dual switching simultaneously in a single‐molecule integrated module. And the multifunctional switching ON/OFF channels can be manipulated in the bulk crystal or unidirectional film by applying an external thermal signal, which shows a high signal‐to‐noise ratio of 2:1 and a strong fatigue resistance. Besides, the dense film maintains the structural retention characteristic after more than 10 000 times of folding over 90°, which is the mark of its real genius as an ultraflexible blue‐light device. This finding will promote the application of blue‐light materials in optoelectronic devices and open up a new era of molecule‐based blue‐light switchable multifunctional materials.

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“…Polymorphs are multiple crystal forms of a given compound and are categorized as either monotropic or enantiotropic in which the higher melting form is or is not (former versus latter) thermodynamically stable at all temperatures below the melting point (Carlton, 2011). The order-disorder enantiotropic phase transitions are triggered by molecular rearrangement in the crystal structure associated with or without a space group change (Asghar et al, 2016;Chia & Quah, 2016;Khan et al, 2015;Quah et al, 2012). The molecules of positional or conformational disordered crystals at the hightemperature phase are transformed into a stable state with single position or conformation at the low-temperature phase (Suzuki et al, 2014).…”

Section: Introductionmentioning

confidence: 99%

Temperature-induced order–disorder structural phase transitions of two-dimensional isostructural hexamethylenetetramine co-crystals

Chia

Quah

2017

Acta Crystallogr Sect B

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Hexamethylenetetramine-benzoic acid (1/2) (HBA) and hexamethylenetetramine-4-methylbenzoic acid (1/2) (HMBA) co-crystals undergo order-disorder structural phase transition from a low-temperature monoclinic crystal structure to a high-temperature orthorhombic crystal structure at the transition temperatures of 257.5 (5) K (Pn ↔ Fmm2) and 265.5 (5) K (P2/n ↔ Cmcm), respectively, using variable-temperature single-crystal X-ray diffraction analysis. The observed phase transitions were confirmed to be reversible first-order transitions as indicated by the sharp endothermic and exothermic peaks in the differential scanning calorimetry measurement. The three-molecule aggregate of HBA and HMBA consists of a hexamethylenetetramine molecule and two benzoic acid or two 4-methylbenzoic acid molecules, respectively. The acid molecules are ordered at the low-temperature phase and are equally disordered over two positions, which are related by a mirror symmetry, at the high-temperature phase. The two-dimensional supramolecular constructs common to both co-crystals are formed by three-molecule aggregates via weak intermolecular C-H...O and C-H...π interactions into molecular trilayers parallel to the ac plane with small XPac dissimilarity indices and parameters. The PIXEL interaction energies of all corresponding molecular contacts were calculated and the results are comparable between HBA and HMBA co-crystals, resulting in similar lattice energies and transition temperatures despite their two-dimensional isostructural relationship. The observed phase transitions of these two energetically similar co-crystals are triggered by similar mechanisms, i.e. the molecular rotator ordering and structural order-disorder transformation, which induced non-merohedral twinning with similar twin matrices in the low-temperature crystal form of both co-crystals.

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Reversible Phase Transition Triggered by Order–Disorder Transformation of Carboxyl Oxygen Atoms Coupled with Distinct Reorientations in [HN(C₄H₉)₃](fumrate)_0.5·(fumaric acid)_0.5

Cited by 20 publications

References 40 publications

N-Methylpyrrolidinium hydrogen tartrate (NMPHT): an above-room-temperature order–disorder molecular switchable dielectric material

N-Methylpyrrolidinium hydrogen tartrate (NMPHT): an above-room-temperature order–disorder molecular switchable dielectric material

The First Molecule‐Based Blue‐Light Optical‐Dielectric Switching Material in Both Hybrid Bulk Crystal and Flexible Thin Film Forms

Temperature-induced order–disorder structural phase transitions of two-dimensional isostructural hexamethylenetetramine co-crystals

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