Halobismuthate/diphenyliodonium hybrids stabilized by secondary hypervalent I(III)⋯X interactions: Structures, optical studies and thermochromisms

Wang, Yukang; Wu, Yanling; Lin, Xiaoyan; Dao-hua, Wang; Zhang, Wenting; Song, Kigook; Li, Hao‐Hong; Chen, Zhirong

doi:10.1016/j.molstruc.2017.09.033

Cited by 25 publications

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References 26 publications

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“…It is worth mentioning that the overall shape of the total DOS as well as selected partial contributions presented here are very similar to those reported previously for other organic–inorganic bismuth bromides. , The corresponding σ ac (1000/ T ) plot (Figure S8b) gave an activation energy of E AC = 1.2 eV (2 E AC ∼ E g ), which well agrees with the value of the transition energy.…”

Section: Resultssupporting

confidence: 88%

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C₂H₅NH₃)₂[BiBr₅]

et al. 2019

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The (C 2 H 5 NH 3 ) 2 [BiBr 5 ] (EBB) crystals adopt the one-dimensional (1D) polymeric anionic form [BiBr 5 ] ∞ 2− , which is preferred by halobismuthates(III) exhibiting polar properties and realized in R 2 MX 5 stoichiometry. Differential scanning calorimetry and dilatometric measurements reveal reversible structural phase transitions: at 160 K (phase I → phase II) and 120 K (phase II → phase III). The resolved crystal structures of EBB show the centrosymmetric space group in phase I (Aeam), polar (Pca2 1 ) in phase II, and polar (Aea2) in phase III. The presence of dielectric hysteresis loops in phases II and III evidence ferroelectric properties. The dielectric response [ε*(ω,T)] of EBB close to 160 K is characteristic of ferroelectrics with a critical slowing down process. The molecular mechanism of a paraelectric−ferroelectric phase transition at 160 K is explained as "order−disorder" (assigned to the dynamics of the ethylammonium cations) and dominating "displacive" (related to strong distortion of the 1D anionic network). The optical band gap obtained from UV−vis measurements is about 2.6 eV. The conduction band minimum is formed by the hybridized Bi 6p and Br 4p states. An analysis of the CSD results for haloantimonates(III) and halobismuthates(III) ferroelectrics characterized by [MX 4 ] − , [M 2 X 9 ] 3− , [MX 5 ] 2− , and [M 2 X 11 ] 5− anions is given.

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Section: Resultssupporting

confidence: 88%

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C₂H₅NH₃)₂[BiBr₅]

et al. 2019

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“…Lead(II) and bismuth(III) halides are the most frequently observed halometallate-base perovskites, whose structural mofits range from 0-D clusters to 3-D networks based on corner-, edge- or face-sharing of MI 6 octahedra. − As far as the choice of host MOF, photoresponsive lanthanide-MOFs are good candidates because of their high sensitivity for external stimuli, − and their functions can be alerted after the encapsulation of halometallates . For example, some electron-deficient organic molecules were incorporated with halometallates to construct donor–acceptor hybrid materials, in which some interesting phenomena such as optical red-shift and effective photo-induced carrier separation can be achieved. − The encapsulation electron-rich halometallates with electron-deficient cationic frameworks will lead to the formation of novel donor–acceptor hybrid materials, which is still in its infancy due to the cation/anion competition. − ,− , Besides, novel photo/electrical properties such as photochromism and photomagnetism have been frequently observed in this kind of hybrid, − which also hint their application in electrical bistability devices .…”

Section: Introductionmentioning

confidence: 99%

Encapsulating Halometallates into 3-D Lanthanide-Viologen Frameworks: Controllable Emissions, Reversible Thermochromism, Photocurrent Responses, and Electrical Bistability Behaviors

Huang

et al. 2019

Inorg. Chem.

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The encapsulation of guests into metal−organic frameworks (MOF) is an efficient strategy to generate novel multifunctional materials with enhanced properties. Herein, four halometallate@MOF composites with formulas of {(Pb 2 I 4 Br 3 ) [(Pr(bpdo) [(La(bpdo) 4 (H 2 O) 2 ] 2 } n (4) (bpdo = 4,4′-bipyridine N,N′-dioxide) were prepared. In these composites, lanthanide-viologen MOF act as matrices, whose cavities were penetrated by halometallates. Consequently, the insertion of electron-rich halometallates into electron-deficient lanthanide-viologen matrices leads to the presence of strong room temperature charge transfer (CT) interactions. Importantly, these composites exhibit enhanced photo/thermal stabilities, controllable white emissions, reversible thermochromisms, and good photocurrent response performances. Specially, the memory devices based on these composites illustrate reversible electrical bistability behaviors, which can be assigned to ohmic and space-charge-limited conduction (SCLC) mechanisms. This kind of composite can be utilized as a multifunctional platform with enhanced stability.

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“…In 3 ( P 1̅, a = 10.1060(4) Å, b = 10.2956(4) Å, c = 11.1394(4) Å, α = 105.030(3)°, β = 101.709(3)°, γ = 117.233(4)°, Z = 1), the anionic part is represented by binuclear bromoantimonate(III) units [Sb 2 Br 10 ] 4– built of two edge-sharing octahedra (Figure , left). This structural type is one of the most common in HMs of group 15 elements. ,− The Sb–Br term and Sb−μ 2 -Br distances are 2.570–2.855 and 2.872–3.333 Å, respectively. In 5 ( P 2 1 / n , a = 20.5536(8) Å, b = 7.2974(2) Å, c = 21.2510(7) Å, β = 117.694(5)°, Z = 4), there are one-dimensional polymeric anions {[SbBr 4 ] n } n − (Figure , right) of type E according to a classification proposed by us earlier .…”

Section: Resultsmentioning

confidence: 98%

Unexpected Polymorphism in Bromoantimonate(III) Complexes and Its Effect on Optical Properties

et al. 2021

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Reactions of [SbBr 6 ] 3− containing HBr solutions with bromide salts of 1,1′-(1,2-ethanediyl)bis(pyridine) (PyC 2 2+ ) or 1,1′-(1,2-ethanediyl)bis(3,5-dimethylpyridine) (3,5-MePyC 2 2+ ) initially result in the formation of the deep orange complexes Cat[SbBr 5 ] (1 and 2), featuring unusual Sb•••Br interactions in the solid state. In the mother liquor, 1 transforms into discrete binuclear (C 2 Py) 2 [Sb 2 Br 10 ], which demonstrates polymorphism (triclinic 3 and monoclinic 4), while 2 transforms into polymeric (3,5-MePy){[SbBr 4 ]} (5). DFT calculations reveal that the system of noncovalent Sb•••Br contacts may be responsible for the appearance of the observed optical properties (unusual deep orange coloring).

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Halobismuthate/diphenyliodonium hybrids stabilized by secondary hypervalent I(III)⋯X interactions: Structures, optical studies and thermochromisms

Cited by 25 publications

References 26 publications

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C₂H₅NH₃)₂[BiBr₅]

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C₂H₅NH₃)₂[BiBr₅]

Encapsulating Halometallates into 3-D Lanthanide-Viologen Frameworks: Controllable Emissions, Reversible Thermochromism, Photocurrent Responses, and Electrical Bistability Behaviors

Unexpected Polymorphism in Bromoantimonate(III) Complexes and Its Effect on Optical Properties

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Halobismuthate/diphenyliodonium hybrids stabilized by secondary hypervalent I(III)⋯X interactions: Structures, optical studies and thermochromisms

Cited by 25 publications

References 26 publications

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C2H5NH3)2[BiBr5]

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C2H5NH3)2[BiBr5]

Encapsulating Halometallates into 3-D Lanthanide-Viologen Frameworks: Controllable Emissions, Reversible Thermochromism, Photocurrent Responses, and Electrical Bistability Behaviors

Unexpected Polymorphism in Bromoantimonate(III) Complexes and Its Effect on Optical Properties

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Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C₂H₅NH₃)₂[BiBr₅]

Ferroelectricity in Ethylammonium Bismuth-Based Organic–Inorganic Hybrid: (C₂H₅NH₃)₂[BiBr₅]