Crystal structure and characterization of the novel hydrogen bonded polar crystal

Wojtaś, M.; ̧gor, A. Ga; Czupiński, O.; Medycki, W.; Jakubas, R.

doi:10.1016/j.jssc.2011.12.020

Cited by 6 publications

(2 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Up to date, there are merely 4 examples in the CCDC database: bisĲpiperazin-1-ium) tetrathiotungstate, 29 piperazinium nitrate, 30 catena-(piperazinium bisĲμ2-selenido)-gallium) 31 and piperazin-1-ium tetrafluoroborate. 27 The crystal under investigation is potentially applicable as a nonlinear optical (NLO) material because of its low cost of synthesis and good thermal stability.…”

Section: Discussionmentioning

confidence: 99%

Polar and antiferroelectric behaviour of a hybrid crystal – piperazinium perchlorate

et al. 2015

View full text Add to dashboard Cite

Monoprotonated piperazinium perchlorate, ĳNH 2 ĲCH 2 ) 4 NH]ĳClO 4 ], appeared to be a novel room temperature polar material (P1). Its acentric symmetry was confirmed by single-crystal X-ray diffraction, second harmonic generation (SHG) and pyroelectric measurements. Differential scanning calorimetry (DSC) measurements revealed a complex sequence of phase transitions above room temperature: I ↔ II at 433/422 K (heating-cooling), II ↔ III at 417/411 K, III ↔ IV at 403/395 K and IV ↔ V at 397 K (the lowest temperature phase transition recorded only upon heating). The characteristic feature of the structure of ĳNH 2 ĲCH 2 ) 4 NH]ĳClO 4 ] is the presence of two parallel cationic chains which are connected with each other by strong N-H⋯N hydrogen bonds. In phase V, these strongly polar non-equivalent chains contribute to spontaneous polarization. 1 H NMR measurements disclosed the reorientational motions of the piperazinium Ĳ[NH 2 ĲCH 2 )NH] + ) cations as well as the proton motion in the N-H⋯N hydrogen bonds along the piperazine chain. Over phase I, the overall motions of the ClO 4 − anions and reorientational motion of cations are postulated. The dielectric response, ε′ĲT), accompanying the PT I ↔ II indicates possible antiferroelectricity in phase II.

show abstract

Section: Discussionmentioning

confidence: 99%

Polar and antiferroelectric behaviour of a hybrid crystal – piperazinium perchlorate

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Molecular–ionic salts, with stoichiometry ratio 1:1-AMX 4 , where [MX 4 ] − is a tetrahedral monoanion, such as perchlorate, tetrafluoroborate, or perrhenate, and A + is a monocation, exhibit ferroic and/or nonlinear optical physical properties. − The AMX 4 materials form the zero-dimensional (0D) molecular–ionic salts. The cations and anions are connected by the electrostatic attraction, e.g .…”

Section: Introductionmentioning

confidence: 99%

Temperature-Stimulus Responsive Ferroelastic Molecular–Ionic Crystal: (C₈H₂₀N)[BF₄]

et al. 2020

View full text Add to dashboard Cite

Molecular−ionic crystals, which are built of organic cations and discrete anionic components with AMX 4 stoichiometry, easily induce structural order−disorder transitions. These phenomena can generate interesting ferroic properties. Herein, we have synthesized and characterized a novel AMX 4 -type crystal, (C 8 H 20 N)-[BF 4 ] (1). Thermal analysis, (DSC, TGA) indicates one structural phase transition (PT) at 257/259 K (cooling/heating, I ↔ II). The structure of 1 has been solved at two temperatures, 120 and 298 K, with single-crystal X-ray diffraction. The high-temperature phase I (1-HT) shows a tetragonal structure with the space group I4/mmm, whereas the low-temperature phase II (1-LT) is monoclinic with the space group P2 1 /a. The PT belongs, thus, to the improper ferroelastic species 4/mmmF2/m with a 4-fold multiplication of the unit cell. All four possible ferroelastic domains of phase II have been identified in polarized light microscopy. The monoclinic deformation has been shown to give rise to a characteristic parquet-like texture preserving integrity of 1. The molecular mechanism of PT involving changes in the cationic and anionic dynamics has been postulated based on measurements of the 1 H and 19 F NMR spin−lattice relaxation times, T 1 , and second-moment, M 2 , and of the dielectric responses. The ac and dc conductivity measurements have been used to determine the transport properties of the charge carriers in 1. The intrinsic features of molecular−ionic crystals, such as the dynamics of molecular motions, structural instability with a lattice-symmetry change, formation of domain patterns, etc., provide a crystal with unique ferroelastic properties. This type of crystal may be useful as an functional material.

show abstract

Structural Phase Transitions and Dielectric Switching in a Series of Organic‐Inorganic Hybrid Perovskites ABX₃ (X=ClO₄⁻ or BF₄⁻)

Sun

Han

Zhang

2017

Chemistry A European J

View full text Add to dashboard Cite

A series of organic-inorganic hybrid perovskites ABX (A=diprotonated 1,4-diazabicyclo[2.2.2]octane or piperazine; B=Na or K ; X=ClO or BF ) has been synthesized. They feature a cubic cage-like host-guest structures of which A is the cationic guest residing in the anionic cage B X , B is the vertex of the cage with variable coordination numbers between six and twelve, and X is the bridging ligand with mono- and/or bidentate coordination modes. The extended Goldschmidt tolerance factor t is used to describe the phase stability of the compounds. Differential scanning calorimetry, variable-temperature structural analyses, and dielectric measurements reveal that order-disorder transitions of the A guest and/or X bridging ligand are supposed to be responsible for structural phase transitions and dielectric switching in the compounds.

show abstract

Crystal structure and characterization of the novel hydrogen bonded polar crystal

Cited by 6 publications

References 32 publications

Polar and antiferroelectric behaviour of a hybrid crystal – piperazinium perchlorate

Polar and antiferroelectric behaviour of a hybrid crystal – piperazinium perchlorate

Temperature-Stimulus Responsive Ferroelastic Molecular–Ionic Crystal: (C₈H₂₀N)[BF₄]

Structural Phase Transitions and Dielectric Switching in a Series of Organic‐Inorganic Hybrid Perovskites ABX₃ (X=ClO₄⁻ or BF₄⁻)

Contact Info

Product

Resources

About

Crystal structure and characterization of the novel hydrogen bonded polar crystal

Cited by 6 publications

References 32 publications

Polar and antiferroelectric behaviour of a hybrid crystal – piperazinium perchlorate

Polar and antiferroelectric behaviour of a hybrid crystal – piperazinium perchlorate

Temperature-Stimulus Responsive Ferroelastic Molecular–Ionic Crystal: (C8H20N)[BF4]

Structural Phase Transitions and Dielectric Switching in a Series of Organic‐Inorganic Hybrid Perovskites ABX3 (X=ClO4− or BF4−)

Contact Info

Product

Resources

About

Temperature-Stimulus Responsive Ferroelastic Molecular–Ionic Crystal: (C₈H₂₀N)[BF₄]

Structural Phase Transitions and Dielectric Switching in a Series of Organic‐Inorganic Hybrid Perovskites ABX₃ (X=ClO₄⁻ or BF₄⁻)