NQR Study of Phase Transition and Cationic Motion in 4-NH2C5H4NHBiBr4·H2O

Niki, H.; Kinjou, Hiroaki; Fukumura, Taichi; Terao, Hiromitsu; Yoshida, Mami; Hashimoto, Masao

doi:10.1007/s10751-005-9096-1

Cited by 5 publications

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References 6 publications

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“…With the difference of the metal and halogen contents, these eight compounds crystallize in five different space groups: Pbca ([4ApyH]BiI 4 ), Pca 2 1 ([4ApyH]Sb 0.5 Bi 0.5 I 4 ), P 2 1 / c ([4ApyH]SbI 4 (100 K) and [4ApyH]BiI 2 Br 2 , [4ApyH]BiBr 4 , and [4ApyH]SbBr 4 (100 K)), I 2/ a ([4ApyH]Sb 0.5 Bi 0.5 I 2 Br 2 and [4ApyH]SbI 2 Br 2 ), and C 2/ c ([4ApyH]SbI 4 (298 K) and [4ApyH]SbBr 4 (298 K)). Both [4ApyH]SbI 4 and [4ApyH]SbBr 4 have the P 2 1 / c phase at 100 K and change to the C 2/ c phase at 298 K. This is due to disorder of the organic amines (Figure S34), which had been reported previously. − It is worth noting that [4ApyH]Sb 0.5 Bi 0.5 I 4 crystallizes in the polar space group Pca 2 1 , while [4ApyH]BiI 4 and [4ApyH]SbI 4 crystallize in central symmetric space groups ( Pbca and P 2 1 / c ). In previous reports, organic amines and halides have been used to control the polarity of metal halides, and this is the first time that doping of the metal ions can also be found to control the polarity of metal halides. , …”

Section: Resultssupporting

confidence: 69%

“…Single-crystal X-ray diffraction data collection for [4ApyH]BiI 4 , [4ApyH]BiI 2 Br 2 , and [4ApyH]BiBr 4 was conducted on a Bruker SMART APEX II CCD diffractometer (Mo, λ = 0.71073 Å), while the crystal data of [4ApyH]Sb 0.5 Bi 0.5 I 4 , [4ApyH]SbI 4 , [4ApyH]Sb 0.5 Bi 0.5 I 2 Br 2 , [4ApyH]SbI 2 Br 2 , and [4ApyH]SbBr 4 were collected on a Rigaku Oxford Diffraction diffractometer (Mo, λ = 0.71073 Å). The structures were solved by direct methods and refined with a full-matrix least-squares technique within the SHELXTL and Olex 2 program packages. , All non-H atoms were refined anisotropically.…”

Section: Methodsmentioning

confidence: 99%

“…Thus, we chose to investigate the structures and optical and electrical properties of a family of 1D Pb-free organic–inorganic hybrids [4ApyH]Sb x Bi 1– x I y Br 4– y , where 4ApyH = 4-aminopyridine monocation. In previous studies, some of these structures have already been reported. − For example, the crystal structures and optical properties of [4ApyH]BiI 4 and [4ApyH]SbI 4 have been reported by Buikin et al., the Sb nuclear quadrupole resonance and 1 H NMR spectroscopies and crystal structure of [4ApyH]SbBr 4 have been studied by Hashimoto et al, and the crystal structure and ferroelectric properties of [4ApyH]SbCl 4 have been studied by Kulicka, Wojtaśa, and Gagor. − However, the effects of mixed metals and halogens on their structures and properties have not been systematically studied. In this paper, the crystal structures of [4ApyH]BiI 4 , [4ApyH]Sb 0.5 Bi 0.5 I 4 , [4ApyH]SbI 4 , [4ApyH]BiI 2 Br 2 , [4ApyH]Sb 0.5 Bi 0.5 I 2 Br 2 , [4ApyH]SbI 2 Br 2 , [4ApyH]BiBr 4 , and [4ApyH]SbBr 4 have been determined by single-crystal X-ray diffraction.…”

Section: Introductionmentioning

confidence: 96%

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Crystal and Band-Gap Engineering of One-Dimensional Antimony/Bismuth-Based Organic–Inorganic Hybrids

Hui

Lin

et al. 2019

Inorg. Chem.

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Hybrid halide perovskites are emerging semiconducting materials with a diverse set of remarkable optoelectronic properties. Besides the widely studied lead halide perovskites, Pb-free metal halides such as Bi-and Sb-containing hybrid organic− inorganic materials have shown potential as semiconductors and have been deemed candidates for optoelectronic devices. Here, we report a series of 1D Sb/Bi-based organic−inorganic hybrid alloys: [4ApyH]Sb x Bi 1−x I y Br 4−y , where 4ApyH stands for the 4-aminopyridine cations. These compounds are assembled by edge-sharing octahedral [MX 6 ] units stabilizing 1D chains with organic cations filled in between. The crystallographic data of eight selected complexes show that [4ApyH]Sb x Bi 1−x I y Br 4−y has at least five phases (space group) with the difference metal and halogen content:and [4ApyH]SbBr 4 (100 K)), I2/a ([4ApyH]Sb 0.5 Bi 0.5 I 2 Br 2 and [4ApyH]SbI 2 Br 2 ), and C2/c ([4ApyH]SbI 4 (298 K) and [4ApyH]SbBr 4 (298 K)). Powder X-ray diffraction shows that the phase of the sample changes with a change of the metal and halogen ratios, and the change law accords with Vegard's law. The optical band gaps are heavily affected by the metal and halide contents, ranging from 1.94 eV for [4ApyH]BiI 4 to 2.73 eV for [4ApyH]SbBr 4 . When Sb substitutes for Bi to form an alloy, the band gap increases from 1.94 for [4ApyH]BiI 4 to 1.67 eV for [4ApyH]SbI 4 , from 2.13 eV for [4ApyH]BiI 2 Br 2 to 2.41 eV for [4ApyH]SbI 2 Br 2 , and from 2.55 eV for [4ApyH]BiBr 4 to 2.73 eV for [4ApyH]SbBr 4 . The conductivity of [4ApyH]Sb x Bi 1−x I 4 increased from ∼1.00 × 10 −15 to 2.14 × 10 −8 S cm −1 with an increase of the Sb content. Solution-deposited thin films of the nine complexes show the same (110) orientation, displaying a parallel growth orientation with respect to the substrate. The devices of [4ApyH]Sb 0.8 Bi 0.2 I 4 and [4ApyH]SbI 4 demonstrated stable open-circuit photovoltages of 0.55 and 0.44 V, steady-state short-circuit photocurrent densities of 1.52 and 1.81 mA cm −2 , and light-to-electrical energy conversion efficiencies of 0.29% and 0.30%, respectively.

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Section: Resultssupporting

confidence: 69%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

See 1 more Smart Citation

Crystal and Band-Gap Engineering of One-Dimensional Antimony/Bismuth-Based Organic–Inorganic Hybrids

Hui

Lin

et al. 2019

Inorg. Chem.

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127I NQR and 1H NMR studies of 4-aminopyridinium tetraiodoantimonate(III); molecular motion and phase transition

Terao¹,

Kai²,

Kita³

et al. 2010

Hfi / Nqi 2010

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127I NQR and 1H NMR studies of 4-aminopyridinium tetraiodoantimonate(III); molecular motion and phase transition

et al. 2010

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The crystals of 4-NH 2 PyHSbI 4 (Py = C 5 H 4 N) have been investigated by means of 127 I NQR, 1 H NMR T 1 and DTA. The crystals can exist in two modifications of β and α(I) at room temperatures. The α(I)-phase is a metastable state which is obtained when the stable β form is heated. The α(I)-phase undergoes a first-order type phase transition of α(I) ↔ α(II) at 272 K (on heating), while the β-phase is stable down to 77 K. Four and two 127 I (m = ±1/2 ↔ ±3/2) NQR lines have been found for the β-and α(II)-phases, respectively. One half of them is assignable to the terminal I atom(s) and the other to the bridging I atom(s) in each phase. All the resonance lines of the α(II)-phase underwent a disappearance above ca. 240 K and no resonance line was observed in the α(I)-phase. The second moment M 2 value of 1 H NMR spectra with 8 G 2 at 290 K shows that the 4-NH 2 PyH + cations reside in the rigid lattice in the β-phase. In contrast, in the α(I)-phase the cation rotates about an axis more symmetric than pseudo threefold axis. The activation energy of 21 kJ mol −1 was estimated for the reorientational motion in the α(I)-phase from the 1 H NMR T 1 measurements. The nature of phase transitions in the 4-NH 2 PyHSbI 4 is discussed in comparison with that in 4-NH 2 PyHSbBr 4 .

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NQR Study of Phase Transition and Cationic Motion in 4-NH2C5H4NHBiBr4·H2O

Cited by 5 publications

References 6 publications

Crystal and Band-Gap Engineering of One-Dimensional Antimony/Bismuth-Based Organic–Inorganic Hybrids

Crystal and Band-Gap Engineering of One-Dimensional Antimony/Bismuth-Based Organic–Inorganic Hybrids

127I NQR and 1H NMR studies of 4-aminopyridinium tetraiodoantimonate(III); molecular motion and phase transition

127I NQR and 1H NMR studies of 4-aminopyridinium tetraiodoantimonate(III); molecular motion and phase transition

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