RSC Advances
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2021
·Vol. 11
·期 17
·10309-10315
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IF 3.361
Kaitong Liu,Jian Han,Junben Huang,Zhonglei Wei,Zhihua Yang,Shilie Pan
Three new iodates SrTi(IO3)6·2H2O, (H3O)2Ti(IO3)6, and SrSn(IO3)6 have been synthesized via a facile hydrothermal method. The three compounds have zero-dimensional crystal structures composed of one [MO6]8− (M = Ti, Sn) octahedron connected with six [IO3]− trigonal pyramids. However, the particular coordination of Sr2+ cations results in distinct arrangements of lone pair electrons in an [IO3]− trigonal pyramid, which leads to large birefringences. More importantly, this work enriches the species crystal chemistry for [M(IO3)6]2− (M = Ti, Sn) clusters-containing iodates.
研究领域:
材料科学
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晶体化学
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PubMed
高影响因子
Inorganic Chemistry Frontiers
·
2024
·Vol. 11
·期 17
·5648-5656
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IF 6.1
Yuhan Hu,Xi Xu,Ruixi Wang,Jingyun Han,Shunsong Zhang,Shuhui Zhan,Jingyu Guo,Li-Ming Wu,Ling Chen
Tin(II)-containing phosphates are promising candidates for designing and studying materials with enhanced birefringence. Herein, we present a novel compound [Sn3OF]PO4 that exhibits significant birefringence (Δnobv. = 0.117 at 546 nm), a five-fold improvement compared to that of the related compound [Sn3F3]PO4 discovered nearly 40 years ago. The remarkable enhancement in birefringence is primarily attributed to the anisotropic [SnO3F]5− structure building unit. By simple regulation of the F/O ratio, the undesirable R3 symmetry in [Sn3F3]PO4 is disrupted. This regulation also realigns the lone pairs, resulting in substantial optical anisotropy.
研究领域:
材料科学
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光学
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DOI
高影响因子
INORGANIC CHEMISTRY
·
2023
·
IF 4.6
Yihao Chen,Lei Zhou,Shuigen Zhou,Donghui You,Haizhou Xiong,Yuhan Hu,Qinlin Chen,Rongxing He,Ming Li
ns2-Metal halide perovskites have attracted wide attention due to their fascinating photophysical properties. However, achieving high photoluminescence (PL) properties is still an enormous challenge, and the relationship between the lattice environment and ns2-electron expression is still elusive. Herein, an organic–inorganic Bi3+-based halide (C5H14N2)2BiCl6·Cl·2H2O (C5H14N22+ = doubly protonated 1-methylpiperazine) with a six-coordinated structure has been successfully prepared, which, however, exhibits inferior PL properties due to the chemically inert expression of Bi3+-6s2 lone-pair electrons. After reasonably embedding Sb3+ with 5s2 electrons into the lattice of (C5H14N2)2BiCl6·Cl·2H2O, the host lattice environment induces the Sb–Cl moiety to change from the original five-coordinated to six-coordinated structure, thereby resulting in a broad-band yellow emission with a PL efficiency up to 50.75%. By utilizing the host lattice of (C5H14N2)2BiCl6·Cl·2H2O, the expression of Sb3+-5s2 lone-pair electrons is improved and thus promotes the radiative recombination from the Sb3+-3P1 state, resulting in the enhanced PL efficiency. This work will provide an in-depth insight into the effect of the local structure on the expression of Sb3+-5s2 lone-pair electrons.
研究领域:
材料科学
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化学
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PubMed
高影响因子
DALTON TRANSACTIONS
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2022
·Vol. 51
·期 38
·14545-14550
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IF 4.569
Alimujiang Yalikun,Kewang Zhang,Jian Han,Zhihua Yang
Enhancement of birefringence is significant since the birefringent materials can create and control polarized light and be used extensively in various advanced optical systems. By optimizing the arrangement of [SbS3] units with stereo-chemical active lone pair electrons, a new quaternary thioantimonate LiSrSbS3 with a large birefringence has been successfully synthesized by a high temperature solid-state reaction method. LiSrSbS3 crystallizes in the monoclinic space group of P21/c. In the structure, the isolated infinite [LiS4] chains and zigzag [SrS6] chains are alternately connected with each other to compose a three-dimensional (3D) framework, and the isolated pyramid [SbS3] units are located between them. To analyze the source of large birefringence, the electronic structure and optical properties of LiSrSbS3 were further investigated by the first-principles method, and the results show that the optimized arrangement [SbS3] trigonal pyramid induces a large birefringence.
研究领域:
材料科学
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光学
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DOI
高影响因子
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES
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2019
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IF 0.961
Steffen Klenner,Judith Bönnighausen,Jingyu Guo,Zhihua Yang,Shilie Pan,Rainer Pöttgen
The crystal structure of diamagnetic borate chloride Sn 2 B 5 O 9 Cl exhibits two crystallographically independent tin sites which both show pronounced lone-pair activity of the tin atoms. This is reflected in substantial quadrupole splitting in the 119 Sn Mössbauer spectrum. The isomer shifts of 3.887(8) and 4.137(7) mm s −1 clearly indicate divalent tin. In agreement with bond valence calculations, the Sn1 atoms have a lower charge and the higher isomer shift, compatible with a higher electron density at the tin nuclei.
研究领域:
材料科学
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物理学
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高影响因子
Science China-Materials
·
2023
·Vol. 66
·期 7
·2795-2802
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IF 8.1
Zheng Zhe-Xiong,Qiu Zhi-Xin,Xie Chao-Hong,Zhang Yang-Ping,Jiang Xiao-Ming,Liu Bin-Wen,Guo Guo-Cong
Strong second-harmonic generation (SHG) and phase-matchable capability at specific transmittance windows are crucial to the real application of nonlinear optical crystals. Herein, an efficient strategy of introducing Pb 2+ with stereochemically active lone-pair electrons into non-phase-match-able Ga 2 Se 3 via enhancing the anisotropy microstructure is first applied to meet phase-matchable SHG intensity requirements, offering a selenide, namely, PbGa 4 Se 7 , which is designed and synthesized with a diamond-like anionic framework, where Pb 2+ cations reside in a parallel arrangement. As expected, PbGa 4 Se 7 possesses a large SHG coefficient of 3.3 times that of AgGaS 2 under the incident laser of 1910 nm. Moreover, PbGa 4 Se 7 displays a high laser-induced damage threshold of 7.0 times that of AgGaS 2 at 2090 nm, which originates from the low anisotropy of thermal expansion coefficient (0.36) and suitable optical band gap (2.1 eV). Theoretical calculations demonstrate that the considerable phase-matchable SHG response of PbGa 4 Se 7 can be attributed to the synergies of tetrahedral GaSe 4 and pyramid PbSe 3 microstructural blocks with additional anisotropy and polarizability.
研究领域:
材料科学
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光学
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高影响因子
Inorganic Chemistry Frontiers
·
2023
·Vol. 10
·期 11
·3367-3374
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IF 7
Chao Zhang,Mao-Yin Ran,Xin Chen,Sheng-Hua Zhou,Hua Lin,Yi Liu
Birefringent crystals are highly desirable for their important applications in optoelectronic fields. However, the rational design of novel birefringent materials with large birefringence (Δn) has always faced great challenges. In this work, a novel quaternary thioarsenate, CsZnAsSe3, has been rationally designed and successfully obtained based on a stereochemically active lone pair (SCALP) induction strategy via the facile surfactant–thermal method. In the structure of CsZnAsSe3, isolated [AsSe3] triangular pyramids and one-dimensional infinite [Zn–Se]∞ chains are alternately connected with each other to generate a two-dimensional [ZnAsSe3]− layer and the charge-balanced Cs+ cations are occupied between them. The introduction of SCALP cations not only induces structural dimension transformation but also significantly improves optical anisotropy. Remarkably, CsZnAsSe3 exhibits a significantly increased Δn (ca. 0.223), which is about 28 times that of the previously reported three-dimensional parent CsZn4Ga5Se12 (ca. 0.008). Moreover, detailed theoretical investigation has aided in the deep understanding of the electronic structure and the source of large Δn. This research offers a useful structural design strategy for discovering new chalcogenides with enhanced Δn in the future.
研究领域:
材料科学
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光学
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高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2024
·
IF 3.9
Kun Ding,Bo Zhuang,Bo-Wen Deng,Zhi-Long Li,Hai-Feng Lu,Zhi-Xu Zhang,Da-Wei Fu
The lone pair electrons in the electronic structure of molecules have been a prominent research focus in chemistry for more than a century. Stable s2lone pair electrons significantly influence material properties, including thermoelectric properties, nonlinear optical properties, ferroelectricity, and electro(photo)catalysis.While major advances have been achieved in understanding the influence of lone pair electrons on material characteristics, research on this effect in organic-inorganic hybrid materials is in its initial stage. In this work, we successfully obtained a novel organic-inorganic hybrid material incorporating Ge with 4s2 lone pair electrons, (MeHDabco)2[GeBr3]4-H2O (MeHDabco = N-methyl-1,4-diazabicyclo[2.2.2]octane) (1). Driven by the stereochemically active lone pair electrons on the Ge2+, 1 crystallizes in the noncentrosymmetric space group P21 at room temperature and exhibits good second harmonic generation (SHG) responses. Interestingly, 1 also shows electrocatalytic activity for the hydrogen evolution reaction due to the existence of lone pair electrons on Ge2+ cations. The electrochemical experiment combined with the DFT calculations revealed the lone pair electrons act as both an active site for proton adsorption and facilitate the ionization of water. This work not only emphasizes the important role of lone pair electrons in material properties and functions but also provides new insight for designing novel Ge-based hybrid materials.
研究领域:
材料化学
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物理化学
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PubMed
高影响因子
INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Lihan Deng,Mengfan Wu,Zhihua Yang,Shujuan Han,Shilie Pan
Sn3B10O17Cl2 was successfully obtained for the first time under the sealed environment and crystallized in the space group Pbcn belonging to the orthorhombic system, which is featured by the fundamental building blocks [B5O11] that are linked to construct a three-dimensional framework with Cl and Sn atoms located inside and at the edge of the channel to balance the charge. Moreover, the optical performance measurement shows that Sn3B10O17Cl2 owns a cutoff edge of about 280 nm. Theoretical study indicates its large optical anisotropy with the birefringence 0.125@546 nm; meanwhile, the structure–performance relationships were analyzed by the first-principle calculation.
研究领域:
材料科学
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光学
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PubMed
高影响因子
INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Yuanyu Yang,Yao Guo,Bingbing Zhang,Ting Wang,Yi-Gang Chen,Xiaohui Hao,Xiaoxiu Yu,Xian-Ming Zhang
The exploration of nonlinear-/linear-optical crystal materials with high performance is an extremely difficult research project. Herein, the two new lead tellurite crystals BaPbTe2O6 and PbVTeO5F were successfully obtained through a facile hydrothermal synthesis strategy. BaPbTe2O6 lies in the noncentrosymmetric (NCS) and chiral orthorhombic space group P212121, featuring a unique ∞1[PbTe2O6] chain consisting of the PbO4 and TeO3 building units, while PbVTeO5F belonging to the centrosymmetric (CS) orthorhombic space group Pbca manifests a 2D layer made up of ∞1[PbO4F2] chains and novel [V2Te2O10F2] clusters. Further, a systematic analysis of lead tellurites finds that the coordination geometries of the Pb atom exert a considerable influence on the connection modes of Pb–O and Te–O building units. BaPbTe2O6 shows a great second-harmonic-generation (SHG) effect of ∼5× the benchmark KH2PO4 (KDP) and a large optical birefringence of 0.086 at 590 ± 3 nm. PbVTeO5F demonstrates a remarkably larger birefringence of 0.142 at 590 ± 3 nm, benefiting from the introduction of the VO5F octahedral unit. Theoretical studies reveal that the large SHG and birefringence in BaPbTe2O6 can be attributed to TeO3 and PbO4 polyhedra with active lone pairs, while the remarkably enlarged birefringence in PbVTeO5F is attributable to the highly distorted octahedral VO5F. The functional orientations of active building units may offer a practical insight into the design of the desired optical functional materials.
研究领域:
材料科学
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光学
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PubMed
高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 35
·20223-20228
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IF 10.733
Dandan Wu,Shaonian Hu,Hongyun Xue,Xiaojuan Hou,Haiwei Du,Gengsheng Xu,Yupeng Yuan
Graphitic carbon nitride (g-C3N4) with pronounced excitation of lone pairs benefits from extended visible light absorption, which thus enhances its photocatalytic hydrogen (H2) generation activity. However, achieving such lone pair excitation in g-C3N4 remains a grand challenge. Here we report on the synthesis of g-C3N4 with remarkable lone pair excitation through thermolysis of protonated melamine via a facile microwave-assisted heating. The g-C3N4 photocatalyst after optimizing the proton concentration offers a highest H2 generation rate of 21.4 μmol h−1, which is nearly 7 times higher than that of g-C3N4 created from unprotonated melamine under identical conditions (3.2 μmol h−1). Furthermore, active H2 generation at 490 nm light irradiation (2.3 μmol h−1) is realized owing to the lone pair excitation. This work shows the great potential of protonation combined with microwave-assisted heating for activating the lone pair excitation in g-C3N4 for increased photocatalytic performance.
研究领域:
材料科学
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光催化
·
能源化学
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DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2025
·
IF 4.7
Chen-Yuan Ma,Yu-Ming Pan,Pei Han,Mei-Hong Duan
Development of new birefringent crystals with enhanced properties remains an ongoing research priority. Through the exploration of guanidinium-containing oxalates with the structural modulation of Pb 2+ and Cl - , a new birefringent crystal, [C(NH 2 ) 3 ]Pb(C 2 O 4 )Cl·H 2 O (GPCCH), was successfully obtained. GPCCH was characterized by two types of π-conjugated building units, which contributes to the coexistence of a wide bandgap of 3.98 eV and a large birefringence of 0.24@546 nm. These findings highlight the synergistic role of π-conjugated building units and partially-chlorinated lead-containing units played in generating fascinating UV birefringent crystals.
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