Raman study of phase transitions in (n-C4H9NH3)2BiCl5

Bator, G.; Provoost, R; Silverans, R. E.; Zeegers‐Huyskens, Th.

doi:10.1016/s0022-2860(97)00129-4

Cited by 16 publications

(7 citation statements)

References 12 publications

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“…This causes weakening of the hydrogen bonding and leads to an increase in the freedom of the reorientational motion of the cations. This was recently confirmed by Raman studies around the α → β-phase transition [22].…”

Section: Discussionsupporting

confidence: 56%

“…The phase transition at 215 K for the β form of the (n-C 4 H 9 NH 3 ) 2 BiCl 5 crystal is dielectrically active ( ε ≈ 4) whereas the phase transitions at 232 and 250 K are invisible. The suggestion based on the DSC measurements that the 215 K phase transition is of an order-disorder type ( S = 5.5 J mol −1 K −1 ) was recently confirmed by a Raman investigation [22]. It turns out that at 215 K the most spectacular changes in the spectra were found in the cation internal vibration region (e.g.…”

Section: Discussionmentioning

confidence: 84%

“…Cl hydrogen bonds. The spectroscopic studies (IR and Raman [22]) show, however, that in the metastable β form of (n-C 4 H 9 NH 3 ) 2 BiCl 5 the n-butylammonium cations form weak NH . .…”

Section: Dielectric Studiesmentioning

confidence: 98%

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On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry, dilatometric and dielectric dispersion studies

Ciapala

Jakubas

Bator

et al. 1997

J. Phys.: Condens. Matter

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Numerous structural phase transitions are detected in new crystals of the nbutylammonium compounds: (n-C 4 H 9 NH 3 ) 2 SbCl 5 , (n-C 4 H 9 NH 3 ) 2 BiCl 5 and (n-C 4 H 9 NH 3 ) 3 SbCl 6 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 (β) form of the (n-C 4 H 9 NH 3 ) 2 BiCl 5 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 mol −1 . The structure of (n-C 4 H 9 NH 3 ) 2 BiCl 5 (α form) has been refined to R = 0.0439 and shows isolated Bi 2 Cl 4− 10 units and two non-equivalent n-butylammonium units. One of these cation possesses dynamical disorder. Most of the phase transitions in the title crystals are classified as an 'order-disorder' type and connected with a reorientational motion of the n-butylammonium cations.

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Section: Discussionsupporting

confidence: 56%

Section: Discussionmentioning

confidence: 84%

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On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry, dilatometric and dielectric dispersion studies

Ciapala

Jakubas

Bator

et al. 1997

J. Phys.: Condens. Matter

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“…In the pristine Bi compound, the very strong band centered at 278 cm −1 and the weak band at 228 cm −1 are assigned to the stretching modes of the terminal and bridging Bi−Cl bonds, respectively. 65 The medium bands observed at 156 and 96 cm −1 are assigned to the Cl−Bi−Cl bending mode and to the lattice vibrations, respectively. 65 However, for the pristine Sb-compound, three Raman bands are observed in the range of 322−227 cm −1 .…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Structural Phase Transition in 0D (3,5-DMP)₂Bi_1–xSb_xCl₅ Metal Halides: Expression of the Lone Pair Effect and Polyhedral Distortion

Sahoo,

Rana,

Samal

2024

Inorg. Chem.

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Low-dimensional Bi/Sb-based organic–inorganic metal halides (OIMHs) have attracted immense attention from the research community because of their structural diversity and efficient luminescence properties. Further understanding of the relationship between the structure and luminescence properties of these materials is of utmost importance for tuning the luminescence properties for various practical applications. Herein, we have synthesized two lead-free Bi/Sb-based novel OIMHs, (3,5-DMP)2BiCl5 and (3,5-DMP)2SbCl5 [(3,5-DMP) = 3,5-dimethylpiperidine], with zero-dimensional (0D) structures and crystallizing in triclinic (P space group) and monoclinic (P21/c space group) crystal systems, respectively. Both the compounds behave as typical semiconductors with indirect optical band gaps of 3.34 and 3.36 eV for pristine Bi and Sb compounds. These compounds exhibit higher environmental and thermal stability at ambient conditions. Gradual substitution of Sb at the Bi site in (3,5-DMP)2Bi1–x Sb x Cl5 resulted in the introduction of structural strain due to the significant expression of the lone pair effect, thus leading to a structural transition from the triclinic to monoclinic phase. The effect of the structural phase transition on the optical properties is also studied in (3,5-DMP)2Bi1–x Sb x Cl5. This work may offer new direction and guidance for exploring various 0D hybrid metal halides and tuning the structures for improvement in the luminescence properties.

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“…Bismuth-halide complexes are of contemporary interest because of their structural diversity and numerous promising physical properties such as dielectric, ferroelectric, ferroelastic, non-linear optical and thermochromism (Bator et al, 1997;Bednarska-Bolek et al, 2000;Sobczyk et al, 1997;Bator et al, 1998). Generally, in these compounds, the BiX 6 octahedra may join to form discrete (i.e.…”

Section: Chemical Contextmentioning

confidence: 99%

Synthesis, crystal structure and Hirshfeld surface analysis of a polymeric bismuthate(III) halide complex, (C₆H₆N₃)₂[BiCl₅]·2H₂O

Boukoum¹,

Aloui²,

Ferretti

et al. 2017

Acta Cryst E

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The synthesis and the crystal structure of a new halide-bridged polymer, namely catena-poly[bis (1,2,3-benzotriazolium) ] n running along the c-axis direction. The 1,2,3-benzotriazolium cations are linked between these polymer chains, via the water molecules, giving rise to left-and right-handed helical chains. Hirshfeld surface analysis and fingerprint plots were used to decode the intermolecular interactions in the crystal network and determine the contribution of the component units for the construction of the three-dimensional architecture.

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Raman study of phase transitions in (n-C4H9NH3)2BiCl5

Cited by 16 publications

References 12 publications

On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry, dilatometric and dielectric dispersion studies

On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry, dilatometric and dielectric dispersion studies

Structural Phase Transition in 0D (3,5-DMP)₂Bi_1–xSb_xCl₅ Metal Halides: Expression of the Lone Pair Effect and Polyhedral Distortion

Synthesis, crystal structure and Hirshfeld surface analysis of a polymeric bismuthate(III) halide complex, (C₆H₆N₃)₂[BiCl₅]·2H₂O

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Raman study of phase transitions in (n-C4H9NH3)2BiCl5

Cited by 16 publications

References 12 publications

On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry, dilatometric and dielectric dispersion studies

On structural phase transitions inn-butylammonium chloroantimonate(III) and chlorobismuthate(III) crystals: x-ray, differential scanning calorimetry, dilatometric and dielectric dispersion studies

Structural Phase Transition in 0D (3,5-DMP)2Bi1–xSbxCl5 Metal Halides: Expression of the Lone Pair Effect and Polyhedral Distortion

Synthesis, crystal structure and Hirshfeld surface analysis of a polymeric bismuthate(III) halide complex, (C6H6N3)2[BiCl5]·2H2O

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Product

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About

Structural Phase Transition in 0D (3,5-DMP)₂Bi_1–xSb_xCl₅ Metal Halides: Expression of the Lone Pair Effect and Polyhedral Distortion

Synthesis, crystal structure and Hirshfeld surface analysis of a polymeric bismuthate(III) halide complex, (C₆H₆N₃)₂[BiCl₅]·2H₂O