Halogen substitution regulates the phase transition temperature and band gap of semiconductor compounds

Li, Hui; Wang, Changfeng; Wu, Ya-Xing; Jiang, Fan; Shi, Chao; Ye, Heng‐Yun; Zhang, Wan-Ying

doi:10.1039/c9cc09477f

Cited by 19 publications

(25 citation statements)

References 28 publications

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“…The average cis angle of 89.99 matches the ideal value of 90 , while the average trans Cl-Bi-Cl angle is 176.60 . The above-described structural parameters for 1 and 2 are comparable with those found in other chloridobismuthates(III) with organic cations showing the same inorganic substructures (Li et al, 2020;Anyfantis et al, 2020).…”

Section: Structures Of 1 Andsupporting

confidence: 81%

Understanding distortions of inorganic substructures in chloridobismuthates(III)

Bujak

2021

Acta Crystallogr Sect B

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The molar ratio variations of organic and inorganic reactants of chloridobismuthates(III) with N,N-dimethylethane-1,2-diammonium, [(CH3)2NH(CH2)2NH3]2+, and N,N,N′,N′-tetramethylguanidinium, [NH2C{N(CH3)2}2]+, cations lead to the formation of four different products, namely, tris(N,N-dimethylethane-1,2-diammonium) bis[hexachloridobismuthate(III)], [(CH3)2NH(CH2)2NH3]3[BiCl6]2 (1), catena-poly[N,N-dimethylethane-1,2-diammonium [[tetrachloridobismuthate(III)]-μ-chlorido]], {[(CH3)2NH(CH2)2NH3][BiCl5]} n (2), tris(N,N,N′,N′-tetramethylguanidinium) tri-μ-chlorido-bis[trichloridobismuthate(III)], [NH2C{N(CH3)2}2]3[Bi2Cl9] (3), and catena-poly[N,N,N′,N′-tetramethylguanidinium [[dichloridobismuthate(III)]-di-μ-chlorido]], {[NH2C{N(CH3)2}2][BiCl4]} n (4). The hybrid crystals 1–4, containing relatively large but different organic cations, are composed of four distinct anionic substructures. They are built up from isolated [BiCl6]3− octahedra in 1, from face-sharing bioctahedral [Bi2Cl9]3− units in 3, from polymeric corner-sharing {[BiCl5]2−} n chains in 2 and from edge-sharing {[BiCl4]−} n chains in 4. The distortions shown by the single [BiCl6]3− polyhedra in 1–4 are associated with intrinsic interactions within the anionic substructures and the organic...inorganic substructures interactions, namely, N/C—H...Cl hydrogen bonds. The first factor is the stronger, which is evident in comparison of the experimentally determined geometrical and calculated distortion parameters for the isolated octahedron in 1 to the more complex inorganic substructures in 2–4. The formation of N—H...Cl hydrogen bonds, in terms of their number and strength, is favoured for 1 and 3 containing relatively easily accessed hydrogen-bond acceptors of isolated [BiCl6]3− and [Bi2Cl9]3− units. The studies of the deviations from regularity of the [BiCl6]3− octahedra within inorganic substructures were supported by a survey of the Cambridge Structural Database, which confirmed the role played by different factors in the variations in geometry of the inorganic anions.

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Section: Structures Of 1 Andsupporting

confidence: 81%

Understanding distortions of inorganic substructures in chloridobismuthates(III)

Bujak

2021

Acta Crystallogr Sect B

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“…3− anions surround by NH 3 CH 2 CH 2 F + cations to form the zero-dimension structure at 272 K, comparing to (EA) 3 BiCl 6 crystallized in the monoclinic space group P2/c. 46 Owing to the independent BiCl 6 3− anions being separated by NH 3 CH 2 CH 2 F + cations and the nearest Bi−Bi distance being 7.53 Å, the intermolecular coupling between anions could be negligible. It can be concluded that anions were mainly connected by cations.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The colorless crystals of (FEA) 3 BiCl 6 were obtained by slow evaporation at room temperature. It adopts an orthorhombic space group P 2 1 2 1 2 with BiCl 6 3– anions surround by NH 3 CH 2 CH 2 F + cations to form the zero-dimension structure at 272 K, comparing to (EA) 3 BiCl 6 crystallized in the monoclinic space group P 2/ c . Owing to the independent BiCl 6 3– anions being separated by NH 3 CH 2 CH 2 F + cations and the nearest Bi–Bi distance being 7.53 Å, the intermolecular coupling between anions could be negligible.…”

Section: Resultsmentioning

confidence: 99%

“…However, nonfluorinated [NH 3 CH 2 CH 3 ] 3 BiCl 6 has no signal of the SHG response, because it crystallized in the centrosymmetric space group. Furthermore, other halogen (Cl/Br) modified compounds [NH 3 CH 2 CH 2 Cl] 3 BiCl 6 and [NH 3 CH 2 CH 2 Br] 3 BiCl 6 also have no signal of SHG response in both phases because they all crystallized in the centrosymmetric space group (Table S1 and Figures S4–S6). Powerful electronegativity, an appropriate van der Waals radius, and the intermolecular forces could be considered an essential cause for triggering the nonlinear optical properties.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, our group also has used this strategy, synthesizing a few compounds with ferroelectricity and improving the T c . , There is still no report on the modified chain ammonium of PT materials for optical properties by using the H/F substitution strategy. Inspired by the design method, we selected halobismuthate materials that have extensive structural diversity and excellent optical characteristics as the research model. − We focus on the recent study that halogen substitution of the organic cation of (CH 3 CH 2 NH 3 ) 3 BiCl 6 can achieve PT temperature regulation, but it could not obtain a noncentrosymmetric (NCS) structure with the required nonlinear optical features. Among the 32 point groups, the second harmonic generation (SHG) was only active in 18 NCS point groups including but not limited to the 10 polar point groups.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Fluorine Substitution in Ethylamine Triggers Second Harmonic Generation in Noncentrosymmetric Crystalline [NH₃CH₂CH₂F]₃BiCl₆

et al. 2020

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The isotope effect usually brings improved performance or new features, such as KD2PO4 and SrTi18O3 inducing a higher phase transition temperature (T c ) and ferroelectricity, respectively. However, the isotope effect seems to work in some limited systems and is usually extremely toxic and unstable. Due to the close van der Waal’s radii and the similar steric parameters, the H/F substitution as an isotope-like effect has been used on spherical amines for designing ferroelectrics. In this work, we reported a study of H/F substitution based on the chain amine in [NH3CH2CH3]3BiCl6. As expected, the substituted compound [NH3CH2CH2F]3BiCl6 successfully achieves the space group transformation from a centrosymmetric to a noncentrosymmetric system, triggering the second-order nonlinear optical properties. Equally importantly, the phase transition temperature increases significantly from 229 to 361.5 K. The crystal structure analysis and 2D fingerprint plots prove that the excellent properties stemmed from the increased force between the organic cations and the inorganic parts as temperature increases. Consequently, this work will open the door for designing a chain amine in hybrid materials to improve the original performance or generate a new performance.

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Chlorine Substitution in Spirocyclic Derivatives Triggers SHG Response in Noncentrosymmetric Crystal

Gao

Zhang

Lun

et al. 2022

Chemistry An Asian Journal

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Organic‐inorganic hybrid phase transition materials with switchable properties have important potential applications in smart devices such as dielectric switches and storage. Nevertheless, it remains challenging to modify molecular structures efficiently to obtain materials simultaneously possessing multiple responsive properties. Herein, different from ordinary halogen substitutions in Metal Halide, we report a halogen regulation design of organic molecular strategy: (ASD)2MnBr4 (ASD=5‐azonia‐spiro [4.5] decane) to (CASD)2MnBr4 (CASD=8‐chloro‐5‐azonia‐spiro [4.5] decane). After organic molecular halogen regulation, the SHG response was excited and the dielectric phase transition temperature (Tc) has also been greatly improved. Furthermore, under the irradiation of UV lamp, both showed green light with quantum yields above 50%. This work is of great significance for further exploration of multifunctional molecular switch materials through halogen modification strategies.

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Halogen substitution regulates the phase transition temperature and band gap of semiconductor compounds

Abstract: Halogen substitution creates a promising platform for designing and optimizing materials with a combination of attractive dielectric and semiconductor properties.

Cited by 19 publications

References 28 publications

Understanding distortions of inorganic substructures in chloridobismuthates(III)

Understanding distortions of inorganic substructures in chloridobismuthates(III)

Fluorine Substitution in Ethylamine Triggers Second Harmonic Generation in Noncentrosymmetric Crystalline [NH₃CH₂CH₂F]₃BiCl₆

Chlorine Substitution in Spirocyclic Derivatives Triggers SHG Response in Noncentrosymmetric Crystal

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Halogen substitution regulates the phase transition temperature and band gap of semiconductor compounds

Abstract: Halogen substitution creates a promising platform for designing and optimizing materials with a combination of attractive dielectric and semiconductor properties.

Cited by 19 publications

References 28 publications

Understanding distortions of inorganic substructures in chloridobismuthates(III)

Understanding distortions of inorganic substructures in chloridobismuthates(III)

Fluorine Substitution in Ethylamine Triggers Second Harmonic Generation in Noncentrosymmetric Crystalline [NH3CH2CH2F]3BiCl6

Chlorine Substitution in Spirocyclic Derivatives Triggers SHG Response in Noncentrosymmetric Crystal

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Fluorine Substitution in Ethylamine Triggers Second Harmonic Generation in Noncentrosymmetric Crystalline [NH₃CH₂CH₂F]₃BiCl₆