0000000001309470
AUTHOR
Ryszard Jakubas
A multiaxial electrical switching in a one-dimensional organic–inorganic (pyrrolidinium)2Cd2I6ferroelectric and photoluminescent crystal
Ferroelectric materials exhibiting more than one polar phase are very attractive in terms of application. The advantage of such materials is temperature-dependent switching between two different ferroelectric states. Here we report on the discovery of a unique, continuous ferroelectric – ferroelectric transformation in (C4H10N)2[Cd2I6], PCdI at 220 K. Thermal measurements suggest that phase transition is close to the continuous one. Both phases belong to the same polar monoclinic Cc space group. Temperature-variable X-ray diffraction measurements of single crystals confirm the polar nature of the two phases (I and II). The anionic network is in the form of [Cd2I6]2− 1D chains, with pyrrolid…
The structure and phase transition of tris(n-propylammonium) enneachlorodiantimonate (III),
The crystal structure of at 298 K has been determined (monoclinic, space group Cc, a = 19.464(2) ?, b = 17.736(2) ?, c = 8.116(2) ?, , Z = 4). The structure consists of one-dimensional polyanionic chains extended along the c-axis, and n-propylammonium cations located in elongated cavities formed by polyanions. The cations are connected to chlorine atoms by hydrogen bonds. Differential scanning calorimetry, the temperature dependence of the lattice parameters and static electric permittivity studies revealed a first-order phase transition at K of an `order - disorder' type. It is related to the ordering of n-propylammonium cations that occurs on decreasing the temperature. Debye-like dispers…
Structure and dynamic dielectric behaviour of ferroelectric [NH2(CH3)2]3Sb2Br9(DMABA)
The crystal structure of DMABA has been determined at 293 and 180 K. It crystallizes in the monoclinic P21/c space group. The structure was refined to R1 = 0.0466 for 1269 independent reflections at 293 K and R1 = 0.038 for 1728 reflections at 180 K. DMABA is isomorphous with the chlorine analogue, DMACA. Its anionic sublattice forms corrugated two-dimensional layers in the bc plane. There are two crystallographically independent, disordered dimethylammonium cations in the crystal structure. One of them occupies cavities inside the polyanionic layers; the other is located between the layers. The temperature dependence of lattice parameters has been determined between 100 and 290 K. The pres…
Structure and properties of tris(tetramethylammonium) nonabromodiarsenate(III), [(CH3)4N]3[As2Br9]
The new tetramethylammonium bromoarsenate(III) crystal [(CH3)4N]3 [As2Br9] has been synthesized and its phase behaviour established by differential scanning calorimetry and dilatometry. Three phase transitions are found: at 346/346 K , at 165/171 K and at 157/165 K on cooling/heating. Single-crystal x-ray diffraction studies of phases I (at 370 K) and II (at 298 K) have shown that the structure comprises discrete [As2Br9]3− anions and disordered [(CH3)4N]+ cations. Phase II crystallizes in the polar space group P31c; its polar nature was confirmed by pyroelectric measurements. Phase I has higher symmetry, P63mc or . Dielectric dispersion measurements revealed a relaxation process in the cry…
Structural characterization, thermal, dielectric and spectroscopic properties of di(n-pentylammonium) pentabromoantimonate(III): [n-C5H11NH3]2[SbBr5]
Abstract The di( n -pentylammonium) pentabromoantimonate(III) compound has been synthesized and studied by means of a single-crystal X-ray diffraction, differential scanning calorimetry, thermal expansion, dielectric and IR techniques. Two solid–solid phase transitions of first order: at 416/388 K and 225/224 K (heating/cooling) have been revealed. The crystal structure of [ n -C 5 H 11 NH 3 ] 2 [SbBr 5 ] has been solved at 298 K, Pna 2 1 (phase II) and at 86 K P 2 1 2 1 2 1 (phase III). The crystal structure is composed of the SbBr 5 2 - anions which form an infinite chain and four independent n -pentylammonium cations. The dielectric studies have been made in the frequency range 500 Hz–1 …
On structural phase transitions in the (C 5 H 12 N) 2 SbCl 5 crystals
Abstract The results of the X-ray (at 295 and 355 K), dilatometric, differential scanning calorimetry and dielectric studies on a new piperidinium crystal, (C5H12N)2SbCl5, are presented. The anionic sublattice of the crystal is built up of infinite (SbCl52−)n chains composed of SbCl63− distorted octahedra connected with each other by corners. In voids of anionic sublattice two crystallographically independent piperidinium cations are located. At 295 K they are both in chair conformation. The compound undergoes three first-order phase transitions at 378.5 K (I→II), 339.5 K (II→III) and 205 K (III→IV). The mechanism of the (II→III) transition (Pna21→P212121) was proposed based on the X-ray da…
STRUCTURE AND PHASE TRANSITIONS IN [C(NH2)3]SbCl6 CRYSTALS
Abstract The crystal structure of [C(NH2)3]SbCl6 at 298 K (monoclinic, C2/m) and 240 K (monoclinic, P21/a) has been determined. The structure consists of isolated SbCl6− anions and guanidinium cations. Differential scanning calorimetry, dilatometric and dielectric studies revealed two structural phase transitions; a first-order one at 351 K and a second-order one at 265 K. One of the two crystallographically non-equivalent anions, SbCl6−(1), disordered in the room temperature phase is postulated to contribute to the phase transition mechanism at 265 K. A ferroelastic domain structure is found below 351 K.
The phase situation and ferroelectric properties in the mixed crystals [4-NH2PyH][SbCl4(1−x)Br4x]
Abstract The group of mixed crystals of general formula: [4-APyH][SbCl4(1−x) Br4x] with x ranging from 0 to 1 was studied by means of differential scanning calorimetry, dilatometry and dielectric spectroscopy. The ferroelectric properties are preserved for mixed crystals with replacement fraction, x, less than 0.30. Moreover, such a substitution of the chlorine atoms by the bromine ones significantly lowers the temperature of the structural phase transition shifting it from 240 K for pure [4-APyH][SbCl4] to about 185 K for the mixed crystals richer in bromine. The dielectric relaxation process exhibited by the mixed crystal with x = 0.90 in the radio-frequency region was analyzed and the ac…
DSC, Dilatometric, Dielectric, and1H NMR Studies of Phase Transitions and Molecular Motions in [N(C2H5)4]3M2Cl9 (M = Sb, Bi) Crystals
Results in the dependence of stoichiometry of obtained tetraethylammonium (TEA) chloroantiomonate and chlorobismuthate salts on the molar ratio of reactants used in the synthesis are presented. Seven tetraethylammonium salts are obtained: (TEA) 6 M 8 Cl 30 , TEAMCI 4 , (TEA) 3 M 2 Cl 9 (M = Sb, Bi) and (TEA) 2 SbCl 5 . Preliminary X-ray diffraction studies on (TEA) 3 M 2 Cl 9 (M = Sb, Bi) show that they are isomorphous, crystallizing at room temperature in monoclinic symmetry. The dilatometric, dielectric, and DSC studies show that (TEA) 3 Bi 2 Cl 9 undergoes two phase transitions at T c2 = 144 K and at T c1 = 322 K while (TEA) 3 Sb 2 Cl 9 undergoes three transitions at T c3 = 185, T c2 = 2…
Structural characterization, thermal, dielectric and vibrational properties of tris(allylammonium) hexabromoantimonate(III), (C3H5NH3)3SbBr6
Abstract The novel inorganic–organic hybrid material, allylammonium hexabromoantimonate(III), (C3H5NH3)3SbBr6, has been synthesized and its structure has been determined by means of the single-crystal X-ray diffraction studies at five temperatures (273, 248, 220, 170 and 100 K). At room temperature the compound crystallizes in the monoclinic space group, C2/m. Its crystal structure is composed of the discrete SbBr 6 3 - anions and three non-equivalent allylammonium, (C3H5NH3)+, cations. In (C3H5NH3)3SbBr6 three solid–solid structural phase transitions are detected: a continuous one at 260/256 K (on heating–cooling) from phase I to II, a discontinuous one at 227/208 K (II→III) and another di…
Crystal structure, phase transition and ferroelectric properties of the [(CH3)3NH]3[Sb2Cl9(1 x)Br9x] (TMACBA) mixed crystals
The paraelectric–ferroelectric phase transition in the [(CH3)3NH]3[Sb2Cl9(1−x) Br9x] (TMACBA) mixed crystals is investigated by the differential scanning calorimetry, dilatometric and dielectric methods. The phase transition is found at 363.5, 362.7, 360.5 and 350.9 K (on cooling) for TMACBA crystals with x = 0, 0.02, 0.17 and 0.42, respectively. The crystal structures of the pure bromine analogue (x = 1), TMABA, and the mixed crystal TMACBA (x = 0.55) are determined at 297 K. TMABA crystallizes in the trigonal space group Rc: a = 15.098(2) A, c = 21.906(4) A, Z = 3, R1 = 0.0393, wR2 = 0.0746. Its structure is built up of discrete Sb2Br93− bioctahedra and disordered trimethylammonium cation…
Structure, phase transitions and molecular dynamics in ferroelastic crystal pyrrolidinium hexachloroantimonate(V), [C4H8NH2][SbCl6]
Abstract The crystal structure of the pyrrolidinium hexachloroantimonate(V), [C4H8NH2][SbCl6], abbreviated PCA, has been determined by means of X-ray diffraction at 300 and 340 K. The space groups are monoclinic P 2 1 / n (phase III) and orthorhombic Pmnb (phase II), respectively. The crystal undergoes two structural phase transitions: first-order type at 356/329 K (heating/cooling) from phase (I) to (II) and second-order type at 323 K from phase (II) to (III). Dielectric studies suggest the plastic crystals behaviour above 356 K (phase I). Proton spin-lattice relaxation time ( T 1 ) and second moment ( M 2 ) of polycrystalline [C4H8NH2][SbCl6] have been determined at 77–370 K, at 90 and 25…
The structure, phase transition and molecular dynamics of [C(NH2)3]3[Sb2Br9]
The crystal structures of [C(NH2)3]3[Sb2Br9] (Gu3Sb2Br9) at 300 K and of [C(NH2)3]3[Sb2Cl9] (Gu3Sb2Cl9) at 90 and 300 K are determined. The compounds crystallize in the monoclinic space group: C 2/c. The structure is composed of Sb2X93− (X = Cl, Br) ions, which form two-dimensional layers through the crystal, and guanidinium cations. In Gu3Sb2Br9 the structural phase transformation of the first-order type is detected at 435/450 K (on cooling/heating) by the DSC and dilatometric techniques. The dielectric relaxation process in the frequency range between 75 kHz and 5 MHz over the low temperature phase indicates reorientations of weakly distorted guanidinium cations. The proton 1H NMR second-…
On structural phase transitions in piperidinium halogenoantimonates(III) and bismuthates(III): X-ray, calorimetric, dilatometric, dielectric and Raman studies
Abstract Three piperidinium analogues: (C5H10NH2)2BiCl5, (C5H10NH2)2BiBr5 and (C5H10NH2)2SbBr5 have been studied by means of differential scanning calorimetry, thermal expansion, dielectric and Raman scattering techniques. Each piperidinium salt undergoes one high-temperature structural phase transition, which has been classified as an “order–disorder” type. All transitions are connected with onset of reorientational motion of the organic cations. The X-ray studies on (C5H10NH2)2BiCl5 show that it crystallises in orthorhombic Pna21 space group. The structure has been refined to R=0.0336. It consists of one-dimensional (BiCl52−)n polyanionic chains and two non-equivalent piperidinium cations…
Structure, phase transitions and molecular motions in ferroelastic (C4H8NH2)SbCl6·(C4H8NH2)Cl
The crystal structure at 293 K of the new pyrrolidinium chloroantimonate (V) analogue, (C4H8NH2)SbCl6(C4H8NH2)Cl, has been determined by x-ray diffraction as monoclinic, space group P21/c, Z = 8. The crystal is built up of isolated SbCl6- anions, two types of inequivalent pyrrolidinium cation and isolated Cl- ions. It undergoes five solid-solid phase transitions: at 351/374 K of first-order type (cooling/heating, respectively), at 356 and 152 K second order and at 135/141 and 105/134 K first order, detected by differential scanning calorimetry, dilatometric and dielectric measurements. The ferroelastic domain structure appears between 152 and 135 K. The proton nuclear magnetic resonance sec…
Crystal structure and dielectric properties of the [(CH3)2NH2]3Sb2(1-x)Bi2xCl9(DMACAB) mixed crystals
Phase transitions in [(CH3)2NH2]3Sb2(1-x)Bi2xCl9 (DMACAB) mixed salts in the composition range 0≤x≤0.41 have been investigated by the pyroelectric method and dielectric measurements over the frequency range from 75 kHz to 900 MHz. The phase situation is additionally confirmed by the differential scanning calorimetry (DSC) and dilatometric techniques. A transition from the paraelectric (PE) to the ferroelectric (FE) phase is observed for crystals with 0≤x≤0.14. Pyroelectric measurements support the presence of polar phases. The dynamic dielectric behaviour of ferroelectric systems is found to be determined by the existence of two independent relaxators. The low-frequency relaxator reveals a …
PHASE TRANSITIONS IN HALOGENOANTIMONATE(V) CRYSTALS: [N(CH3)4]SbCl6 AND [N(C2H5)4]SbCl6
Abstract New crystals of the family of alkylammonium chloroantimonates(V), [N(CH 3 ) 4 ]SbCl 6 and [N(C 2 H 5 ) 4 ]SbCl 6 , have been grown and systematically studied. X-ray studies show that [N(C 2 H 5 ) 4 ]SbCl 6 is composed of isolated cations and ideal SbCl 6 − octahedra. Differential scanning calorimetry, dilatometric and dielectric measurements reveal structural phase transitions in [N(CH 3 ) 4 ]SbCl 6 and [N(C 2 H 5 ) 4 ]SbCl 6 of first order at 236 and 345 K, respectively. The measurements of 1 H-NMR spin-lattice relaxation times, T 1 , show that mechanism of the phase transitions in [N(CH 3 ) 4 ]SbCl 6 and [N(C 2 H 5 ) 4 ]SbCl 6 is due to the reorientations of the tetraalkylammoniu…
The structure and phase transition of mixed crystals
The phase transition and molecular motions of methylammonium cations are studied in the temperature range from 110 to 450 K in the (x = 0.22, 0.345) (MACAB) crystal by x-ray DSC, dilatometric, dielectric and NMR techniques. It is shown that MACAB (x = 0.22) undergoes a structural phase transition at 222 K. The second moment of the NMR line () and the temperature dependence of spin lattice relaxation time () results are interpreted in terms of ( ion dynamics. In the high-temperature phase (I) the cations undergo isotropic reorientations. In the low-temperature phase (II) only one of three cations is still disordered, whereas the two others perform a type of reorientation about their C - N ax…
On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry, dilatometric and dielectric dispersion studies
Numerous structural phase transitions are detected in new crystals of the n-butylammonium compounds: , and by means of differential scanning calorimetry, dilatometric and dielectric dispersion (1 kHz - 1 MHz) studies. For the transitions the basic thermodynamic data are determined. Interesting dielectric properties are found in a metastable form of the crystals. Debye-like dispersion of the electric permittivity between 30 and 800 MHz is observed around the 310 K phase transition for this crystal. The activation energy of the reorientation of the n-butylammonium cations is found to be 16 kJ . The structure of ( form) has been refined to R = 0.0439 and shows isolated units and two non-equiva…
Crystal structure, dielectric properties and molecular motions in ( i -C 4 H 9 NH 3 ) 3 Bi 2 Br 9
Abstract The crystal structure of ( i -C 4 H 9 NH 3 ) 3 Bi 2 Br 9 at room temperature has been determined and refined to R =0.036. The crystal is orthorhombic, space group Ama 2. The structure is built up of the i -butylammonium cations and isolated Bi 2 Br 9 3− anions. The complex dielectric permittivity along the a -axis has been measured between 500 Hz and 1000 MHz in the vicinity of two phase transitions at 252 and 263 K. The dielectric response close to 252 K is well described by the Debye equation. The activation energy of the reorientation of the i -butylammonium cations is found to be 0.68 eV. The temperature dependencies of the proton relaxation time T 1 and of the second moment of…
Structure and phase transitions in guanidinium halogenobismuthates(III)
Abstract Differential scanning calorimetry (DSC), dilatometric and dielectric measurements have been used to study the phase transitions in [C(NH2)3]3BiBr6. The [C(NH2)3]3BiBr6 crystal undergoes four phase transitions: at 419, 429, 475 and 495 K (on heating). The high-temperature phase transition is clearly of first-order type and its high entropy effect allows classifying it as of the order–disorder type. X-ray diffraction studies showed that [C(NH2)3]3BiBr6 crystallises in monoclinic, centrosymmetric space group, C2/c. The anionic sublattice is composed of isolated BiBr63− octahedra. The infrared between 100 and 350 K and Raman spectra at room temperature in the frequency range related to…
Structure and properties of 2-cyanopyridinium perchlorate [2-CNPyH][ClO4]
The crystal structure of 2-cyanopyridinium perchlorate, [2-CNPyH][ClO4], has been determined at 100 (phase II) and 293 K (phase I). It is monoclinic P 21 at 100 K and orthorhombic P 212121 at 293 K. The dynamic properties of the crystal were studied by differential scanning calorimetry, dilatometry, pyroelectric, dielectric, proton (1H NMR), chlorine (35Cl NMR) magnetic resonance spectroscopies and the infrared method. The crystal undergoes a structural phase transition () at 170 K characterized by a complex mechanism involving both 'order–disorder' and 'displacive' contributions. It reveals pyroelectric properties below 170 K. The dielectric relaxation existing over phase I is due to the m…
Structure and phase transitions in the ferroelastic [C(NH2)3]3Bi2Br9crystal
Differential scanning calorimetry, dilatometric, dielectric and linear birefringence measurements have been used to study the ferroelastic [C(NH2)3]3Bi2Br9 crystal. The x-ray studies showed that it crystallizes at room temperature in the monoclinic symmetry, space group P21/m. The crystal undergoes a complex sequence of phase transitions: at 311 K, 333.5 K, 350 K, 415 K and 425 K. All phase transitions were found to be of first order type. The ferroelastic domain structure is maintained from room temperature up to 425 K. The temperature measurements of the linear birefringence and optical observations suggest the tetragonal symmetry of the parent paraelastic phase above 425 K.
Crystal structure, phase transitions and ferroelastic properties of [(CH3)2NH2]3[Bi2Cl9]
Abstract A sequence of structural phase transitions in [(CH3)2NH2]3[Bi2Cl9] (DMACB) is established on the basis of differential scanning calorimetry (DSC) and dilatometric studies. Four phase transitions are found: at 367/369, 340/341, 323/325 and 285/292 K (on cooling/heating). The crystal structure of DMACB is determined at 350 K. It crystallizes in monoclinic space group P21/n: a=8.062(2), b=21.810(4), c=14.072(3) A, β=92.63(3)°, Z=4, R1=0.0575, wR2=0.1486. The crystal is built of the double chain anions (“pleated ribbon structure”) and the dimethylammonium cations. Dielectric studies in the frequency range 75 kHz–900 MHz indicate relatively fast reorientation of the dimethylammonium cat…
Phase transitions in i-butylammonium halogenoantimonate(III) and bismuthate(III) crystals
Abstract Differential scanning calorimetry, dielectric, thermal expansion, infrared and preliminary X-ray diffraction studies on i-butylammonium halogenoantimonate(III) and bismuthate(III) crystals are reported. All crystals: (i-C4H9NH3)2BiCl5, (i-C4H9NH3)2SbBr5, (i-C4H9NH3)3BiCl6, (i-C4H9NH3)3Bi2Br9, (i-C4H9NH3)3Sb2Br9, show one or more structural phase transitions of first order type. The values of the transition entropies suggest that the most of the phase transitions are of the order-disorder type. The infrared studies confirmed the contribution of the i-butylammonium cations in the phase transition mechanism.
1H NMR, DSC, dielectric, and dilatometric studies of phase transitions and molecular dynamics in N (C2H5)4SbCl4
The results of dielectric, dilatometric, 1H NMR, and DSC studies on N(C2H5)4SbCl4 crystals are presented. The title compound undergoes two phase transitions at Tc1 = 272 K reversible of first order and at Tc2 = 393 K irreversible. The values of transition entropies and enthalpies are compared with those of other tetraethylammonium halogenoantimonates and bismuthates (III). The spin-lattice relaxation times and the values of the second moments of the 1H NMR line for the N(C2H5)4SbCl4 crystal are measured in the temperature range of 70 to 400 K. Two minima of T1 are observed. They are attributed to CH3 group reorientations. The activation energies for the processes are determined.
Structural characterization, thermal, dielectric, vibrational properties and molecular dynamics of (C5H5NH)3BiCl6
Abstract (C5H5NH)3BiCl6 crystallizes at room temperature in the triclinic space group P 1 ¯ . The crystal is built up of the separated BiCl 6 3 - octahedral anions and pyridinium cations. Differential scanning calorimetry (DSC) and dilatometric measurements disclose structural phase transition of first-order type at 265/302 K (cooling/heating). The dielectric investigations reveal a step-wise change of the electric permittivity at Tc characteristic of the crystals with the high-temperature plastic-like phase. Temperature-dependent infrared spectra for polycrystalline samples have been taken between 20 and 306 K to clarify the cation dynamics contribution to the mechanism of the phase transi…
CCDC 2070978: Experimental Crystal Structure Determination
Related Article: Magdalena Rok, Bartosz Zarychta, Andrzej Bil, Joanna Trojan-Piegza, Wojciech Medycki, Andrzej Miniewicz, Anna Piecha-Bisiorek, Agnieszka Ciżman, Ryszard Jakubas|2021|J.Mater.Chem.C|9|7665|doi:10.1039/D1TC01526E
CCDC 2070979: Experimental Crystal Structure Determination
Related Article: Magdalena Rok, Bartosz Zarychta, Andrzej Bil, Joanna Trojan-Piegza, Wojciech Medycki, Andrzej Miniewicz, Anna Piecha-Bisiorek, Agnieszka Ciżman, Ryszard Jakubas|2021|J.Mater.Chem.C|9|7665|doi:10.1039/D1TC01526E