scholarly journals Above Room Temperature Reversible Phase Transition Induces Distinct Dielectric and Nonlinear Optical Switching Response Behavior in Crown-Ether-Based Supramolecular Clathrate

Crystals ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 184 ◽  
Author(s):  
Jing Jing ◽  
Fan Jiang ◽  
Yan-Li Wei ◽  
Chao Shi ◽  
Heng-Yun Ye ◽  
...  

Stimuli-responsive materials with coexisting nonlinear optical (NLO) and dielectric properties are technologically important, which enable simultaneous conversion of optoelectronic properties between different states under external stimuli. By rationally screening guest cations (C6H5NF2)+ in the crown-ether inclusion system, we synthesized a crown-ether supramolecular compound [(C6H5NF2)(18-crown-6)][PF6] (1). Differential scanning calorimetry (DSC) showed that 1 undergoes a reversible phase transition above room temperatures (305 K/292 K), with a thermal hysteresis of 13 K. Temperature-dependent dielectric and NLO measurements show that the compound exhibits two distinct switching response behaviors. Structural analysis indicates that the order–disorder change of the host molecule 18-crown-6 and the guest organic cation during the phase transition induces the dielectric and NLO switching behavior of the compound.

2018 ◽  
Vol 54 (58) ◽  
pp. 8076-8079 ◽  
Author(s):  
Yan-Li Wei ◽  
Jing Jing ◽  
Chao Shi ◽  
Heng-Yun Ye ◽  
Zhong-Xia Wang ◽  
...  

[(C6H5NF2)(18-crown-6)][HClO4] is a novel high-temperature dielectric and nonlinear optical switching material based on crown ether clathrates.


Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 507 ◽  
Author(s):  
Tony Tiainen ◽  
Marina Lobanova ◽  
Erno Karjalainen ◽  
Heikki Tenhu ◽  
Sami Hietala

Nanodiamonds (NDs) can considerably improve the mechanical and thermal properties of polymeric composites. However, the tendency of NDs to aggregate limits the potential of these non-toxic, mechanically- and chemically-robust nanofillers. In this work, tough, flexible, and stimuli-responsive polyelectrolyte films composed of cross-linked poly(butyl acrylate-co-dimethylaminoethyl methacrylate) (P(BA-co-DMAEMA)) were prepared by photopolymerization. The effects of the added carboxylate-functionalized NDs on their mechanical and stimuli-responsive properties were studied. When the negatively charged NDs were added to the polymerization media directly, the mechanical properties of the films changed only slightly, because of the uneven distribution of the aggregated NDs in the films. In order to disperse and distribute the NDs more evenly, a prepolymerized polycation block copolymer complexing agent was used during the photopolymerization process. This approach improved the mechanical properties of the films and enhanced their thermally-induced, reversible phase-transition behavior.


2010 ◽  
Vol 66 (3) ◽  
pp. 387-395 ◽  
Author(s):  
Heng-Yun Ye ◽  
Li-Zhuang Chen ◽  
Ren-Gen Xiong

Pyridinium-3-carboxylic acid perchlorate was synthesized and separated as crystals. Differential scanning calorimetry (DSC) measurements show that this compound undergoes a reversible phase transition at ∼ 135 K with a wide hysteresis of 15 K. Dielectric measurements confirm the transition at ∼ 127 K. Measurement of the unit-cell parameters versus temperature shows that the values of the c axis and β angle change abruptly and remarkably at 129 (2) K, indicating that the system undergoes a first-order transition at T c = 129 K. The crystal structures determined at 103 and 298 K are all monoclinic in P21/c, showing that the phase transition is isosymmetric. The crystal contains one-dimensional hydrogen-bonded chains of the pyridinium-3-carboxylic acid cations, which are further linked to perchlorate anions by hydrogen bonds to form well separated infinite planar layers. The most distinct differences between the structures of the higher-temperature phase and the lower-temperature phase are the change of the distance between the adjacent pyridinium ring planes within the hydrogen-bonded chains and the relative displacement between the hydrogen-bonded layers. Structural analysis shows that the driving force of the transition is the reorientation of the pyridinium-3-carboxylic acid cations. The degree of order of the perchlorate anions may be a secondary order parameter.


1998 ◽  
Vol 54 (5) ◽  
pp. 663-670 ◽  
Author(s):  
R. A. Edwards ◽  
A. J. Easteal ◽  
O. P. Gladkikh ◽  
W. T. Robinson ◽  
M. M. Turnbull ◽  
...  

At 228 K crystals of ZnI2(dmf)2 show a reversible phase transition which does not disrupt the lattice. Above the transition temperature the space group is C2/c and the cell contains eight symmetrically equivalent molecules. Cooling to below the transition temperature has little effect on the cell parameters or on the Zn- and I-atom positions, but the space group is now P21/n and the asymmetric unit comprises two conformationally different molecules. These arise from cooperative rotations of either ca +25 or −43° about the Zn—O bond of one of the dmf ligands in the high-temperature form. This displacive transition involves large movements of some atoms. The corresponding chloride and bromide are isomorphous with the higher temperature C2/c form, but it is only with the iodide that the weaker intermolecular forces permit the unusual phase change. The transition has been followed by differential scanning calorimetry, which gives an enthalpy change of 1.44 (5) kJ mol−1.


2018 ◽  
Vol 47 (11) ◽  
pp. 3851-3856 ◽  
Author(s):  
Yi Liu ◽  
Hai-Tao Zhou ◽  
Shao-Peng Chen ◽  
Yu-Hui Tan ◽  
Chang-Feng Wang ◽  
...  

Compound 1 shows apparent step-like dielectric changes near the phase transition, which are triggered by the synergetic rotation motion of 18-C-6 crown ether cycles and hexafluorophosphate anions.


ChemInform ◽  
2005 ◽  
Vol 36 (14) ◽  
pp. no-no
Author(s):  
Shin-ichi Ohkoshi ◽  
Tomoyuki Matsuda ◽  
Hiroko Tokoro ◽  
Kazuhito Hashimoto

2006 ◽  
Vol 111 ◽  
pp. 55-58
Author(s):  
L.L. Guo ◽  
Y.D. Dai ◽  
H.X. Liu ◽  
Shi Xi Ouyang

This paper focuses on the structural change and the thermochromism of the phase transition of the hybrid (C12H25NH3)2FeCl4. The temperature and the structures of the phase transition is investigated by a thermal gravimetry (TG) and differential scanning calorimetry (DSC), an infrared spectra (IR) and X-ray diffraction (XRD) patterns. The UV adsorption spectra account for the thermochromism. The results suggest that the reversible phase transition arises from the structural changes of the organic chains. The thermochromism is presumably due to the electrons redistribution on the levels and to the energy transition to translational and rotational motions of the organic chains.


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