Ethylenediamine as a bridging ligand: structure solution of two cadmium(II)-based coordination polymers from powder diffraction data

Putaj, Piotr; Gaweł, Bartłomiej; Łasocha, Wiesław

doi:10.1017/s0885715613000146

Cited by 2 publications

(2 citation statements)

References 17 publications

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“…The CdCl 6 octahedron displays a slight distortion, with Cd–Cl bond distances in the range 2.534 to 2.769 Å and adjacent Cl atoms’ angles Cl–Cd–Cl varying from 85.92° to 86.72° or 93.76° to 93.89° (Table S1). The geometric parameters are comparable to those found in other chlorocadmate(II) analoges. − It is noteworthy that the NH 3 + head of the CMA cation makes weak hydrogen bonds to two bridging and one terminal Cl atom with donor–acceptor distances of 3.373, 3.543, and 3.251 Å, respectively (Table S2). The characteristic feature of such weak interactions is that they can be easily broken, and then formed alternatively. − In crystals, such a transformation can result in phase transitions.…”

Section: Resultssupporting

confidence: 70%

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Liao

Wang

et al. 2016

Crystal Growth & Design

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Following our recent finding of interesting dielectric and ferroelectric properties in semiconducting organic−inorganic layered perovskites (benzylammonium) 2 PbCl 4 and (cyclohexylammonium) 2 PbBr 4−4x I 4x (x = 0−1), we designed a new layered perovskite-type crystal (cyclohexylmethylammonium) 2 CdCl 4 . By systematic characterizations, including differential scanning calorimetry measurements, dielectric measurements, and variable-temperature structural analysis, this crystal was found to undergo a reversible first-order phase transition at around T c = 342 K. The origin of the phase transition is associated with the order− disorder change of the organic cation as expected. The phase transition is accompanied by the anticipated large dielectric constant change and remarkable dielectric anisotropy. These dielectric performances reveal potential application of the crystal as a high-temperature dielectric material. More interesting dielectric crystals are expected to be tailored in the future by taking advantage of the richness of layered perovskites. ■ INTRODUCTIONOwing to the high potential of producing materials with novel properties, organic−inorganic hybrid compounds are currently a hot topic of research. 1−5 Recently, their study was extended to structural phase transitions, and a few interesting phase transition properties were found. 6−12 The key components are the included organic cations, which have a large degree of motion in the cavities enclosed by the inorganic parts, exhibit dynamical disorder at relatively high temperatures, and become ordered below particular temperatures, giving rise to symmetry breaking and structural phase transitions. 13−16 Structural phase transitions in crystals are generally accompanied by changes of physical properties and, in many cases, can lead to intriguing physical properties, such as ferroelectric, dielectric, and electromechanical properties. 17,18 Therefore, the design of organic−inorganic hybrid crystals with structural phase transitions is very important, not only for the theoretical study of structure−property relationships, but also for the exploration of novel physical properties. 19−22 We have recently demonstrated that structural phase transitions in two-dimensional (2D) lead-halide layered perovskites can lead to interesting ferroelectric and dielectric properties, which produces molecular semiconducting ferroelectricity. 23,24 2D metal-halide layered perovskites with the general formula (R-NH 3 ) 2 MX 4 , where R is any alkyl or aromatic group and M is any divalent metal, have been intensely studied in the last two decades, because these crystals exhibit a number of appealing features suitable for a wide range of applications, such as solid-state batteries, ionic conductors, sensors, photovoltaic cells, luminescent devices, and so on. 25−28 Combination of the phase transition properties and physical properties of the 2D perovskites may lead to new materials and devices for photovoltaics, spintronics, and electrical-mechanical sensing. However, the study i...

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Section: Resultssupporting

confidence: 70%

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Liao

Wang

et al. 2016

Crystal Growth & Design

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“…It is known that transition metal halides Me(tr)X 2 (Me(tr) and X denote any transition metal and halogen atom) easily react with amines forming compounds with interesting architectures . Among amines, fluorine‐substituted aniline is particularly interesting, because beside coordination bonds with Me(tr), π–π interactions and hydrogen bonds can be formed.…”

Section: Introductionmentioning

confidence: 99%

Powder diffraction and synchrotron radiation, a powerful tool in the investigation of new compounds: CdBr₂(3‐fluoroaniline)₂ and CdBr₂(4‐fluoroaniline)₂

2015

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Using synchrotron powder diffraction data, two new complexes of CdBr 2 with 3-fluoroaniline and 4-fluoroaniline were fully characterised with regard to their structure. Their crystal structures were solved and refined by means of powder diffraction techniques. The investigated materials belong to the group of hybrid inorganic-organic coordination polymers. The structures of both compounds are created by the same type, infinite chains formed by CdBr 4 N 2 octahedra. Each cadmium cation is surrounded by four Br À anions, and two N atoms from two fluoroaniline molecules.The obtained structural data enable us to investigate the influence of the position of the F atom in the aniline ring on the crystal structure, as well as to interpret its thermal stability.

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Ethylenediamine as a bridging ligand: structure solution of two cadmium(II)-based coordination polymers from powder diffraction data

Cited by 2 publications

References 17 publications

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Powder diffraction and synchrotron radiation, a powerful tool in the investigation of new compounds: CdBr₂(3‐fluoroaniline)₂ and CdBr₂(4‐fluoroaniline)₂

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Ethylenediamine as a bridging ligand: structure solution of two cadmium(II)-based coordination polymers from powder diffraction data

Cited by 2 publications

References 17 publications

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)2CdCl4

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)2CdCl4

Powder diffraction and synchrotron radiation, a powerful tool in the investigation of new compounds: CdBr2(3‐fluoroaniline)2 and CdBr2(4‐fluoroaniline)2

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Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Design and Prominent Dielectric Properties of a Layered Phase-Transition Crystal: (Cyclohexylmethylammonium)₂CdCl₄

Powder diffraction and synchrotron radiation, a powerful tool in the investigation of new compounds: CdBr₂(3‐fluoroaniline)₂ and CdBr₂(4‐fluoroaniline)₂