DALTON TRANSACTIONS
·
2022
·Vol. 51
·期 39
·15074-15079
·
IF 4.569
Xing Ye,Wenhui He,Jing Wei,Zhenhong Wei,Xiuli You,Hu Cai
The excellent properties of host–guest crown ether inclusions in phase transition, dielectric and second-order nonlinear optical properties have attracted much attention. In this paper, we successfully designed and prepared two novel host–guest crown ether supramolecules [(DFBA)(15-crown-5)]X (X = ClO4−, 1; ReO4−, 2) by reactions of 2,6-difluorobenzylamine (DFBA) with 1,4,10,13-pentaoxacyclopentadecane (15-crown-5) in HClO4, or HReO4 aqueous solution. By the introduction of difluoro-substituted benzylamine as a guest cation, the phase transition temperatures are greatly increased to 377 K for 1 and 391 K for 2. More importantly, the space group of 1 has changed from centrosymmetric (CS) P2/c to the non-centrosymmetric (NCS) Pca21 in 2 when substituting perchlorate (ClO4−) with the larger and heavier perrhenate (ReO4−), which leads to 2 showing a switchable and stable second-harmonic generation (SHG) effect. According to the principle of momentum matching between a cation and anion, the perrhenate group increases the energy barrier of the molecular thermal motion, which not only significantly increases the phase transition temperature of 2 but also causes it to be frozen and crystallized in a NCS space group at room temperature. This research demonstrates that a polar molecule can adjust the suitability of anions and cations inside the crystal by practical chemical means.
研究领域:
材料化学
·
晶体学
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 24
·10235-10243
·
IF 3.5
Yibo Cui,Jindong Cao,Jiawei Lin,Chunxiao Li,Jiyong Yao,Kunjie Liu,An Hou,Zhongnan Guo,Jing Zhao,Quanlin Liu
Organic–inorganic metal halides (OIMHs) have drawn considerable attention due to their remarkable optoelectronic properties and substantial promise for nonlinear optical applications. In this research, phenazine has been selected as the organic cation because of its π-conjugated feature. Three compounds, (C12H9N2)PbCl3, (C12H9N2)SbCl4, and (C12H9N2)2InBr4·Br, were synthesized. Initial space group assignments were centrosymmetric for (C12H9N2)PbCl3 and (C12H9N2)SbCl4. However, under 1550 nm laser excitation, (C12H9N2)PbCl3 and (C12H9N2)SbCl4 exhibited second harmonic generation intensities ∼1.7 times greater than that of the benchmark KH2PO4. Structural reevaluation ultimately confirmed non-centrosymmetric P1 and P21 space groups for (C12H9N2)PbCl3 and (C12H9N2)SbCl4, respectively. Upon excitation at 335 nm and 470 nm, (C12H9N2)PbCl3, (C12H9N2)SbCl4, and (C12H9N2)2InBr4·Br emit fluorescence at room temperature. (C12H9N2)2InBr4·Br exhibits reversible phase transitions, showing potential for phase change energy storage. Our research underscores the critical role of comprehensive experimental validation in determining the precise crystallographic space groups and reveals the extensive potential of OIMHs as versatile candidates for advanced optoelectronic applications.
研究领域:
材料科学
·
光电
·
晶体学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Chem
·
2024
·
IF 19.1
Shuqi Wang,Hao Chen,Tianyu Zhong,Quanzheng Deng,Shaobo Yang,Yuanyuan Cao,Yongsheng Li,Lu Han
Gyroid (G) surfaces, the most famous naturally occurring triply periodic hyperbolic surfaces, are well known for their amazing properties closely associated with their intriguing symmetries. Although mathematicians and physicists are devoted to exploring new G surface family members, it remains a mystery whether any novel symmetrical G substructure can be experimentally validated beyond its well-known cubic-symmetrical systems. Herein, we report a tetragonal G substructure (shifted tG) obtained from a cooperative binary self-assembly system consisting of polystyrene- b -poly(acrylic acid) and cetyltrimethylammonium bromide. Shifted tG features periodic distributions of uneven matrix thicknesses with local concave free energies, exhibits an extraordinarily shifted double-gyroidal network with a low-symmetry space group of I 4 1 / a (no. 88), and possesses shifting-degree-dependent photonic band gaps that are never present in its unshifted cubic-symmetrical counterparts. The emergence of new G structures demonstrates a new frontier in the minimal surface subject, crucial for its exploration and innovation.
研究领域:
材料科学
·
表面科学
✓ 已验证
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2022
·
IF 3.656
Hui Yang,Ziyu Wang,Cuixia Xu,Yuan Lin,Guoliang Liu
The first example of lanthanide borate-sulfate compound, namely, La 2 B 3 O 4 (OH) 3 (SO 4 ) 2 has been obtained through hydrothermal synthesis , which belongs to polar space group Pna 2(1) (No. 33). Its structure possesses double lanthanum sulfate layers in the ab plane in which the lanthanide ions are bridged by SO 4 tetrahedra. These layers are further cross-linked by borate chains into the final 3D framework. It is noteworthy that this compound is the first lanthanide borate-sulfate which crystalizes in polar space group and it displays second-harmonic generation (SHG) signal of about 0.1 times that of KH 2 PO 4 . The SHG coefficient of the compound is ascribed to the synergistic effect of SO 4 units and borate units. Meanwhile, distorted LaO x polyhedra also play an important role in the contribution to SHG response.
研究领域:
材料科学
·
晶体学
✓ 已验证
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2022
·
IF 3.656
Gang-Xiang Liu,Yu-Long Wei,Li-Nan Zhang,Wenlong Liu,Sheng-Ping Guo,Ru-Ling Tang
Phosphites have attracted extensive attention for their abundant open-frameworks and special performances. Here, three inorganic indium phosphites, namely In 2 (HPO 3 ) 3 (H 2 O) (1), In 2 (HPO 3 ) 3 (H 2 O) 3 ·(H 2 O) (2) and NH 4 [In(HPO 3 ) 2 ] (3), have been obtained via facile hydrothermal reactions . 1 and 2 crystallize in the same polar space group P 2 1 , and 3 crystalizes in the polar space group of P 63 mc . Isolated HPO 3 tetrahedra connect to twisted InO 6 octahedra via corner-sharing forming neutral 3D {In 2 (HPO 3 ) 3 (H 2 O)} ∞ and {In 2 (HPO 3 ) 3 (H 2 O) 3 } ∞ as well as 2D [In(HPO 3 ) 2 ]- ∞ frameworks for 1 – 3 , respectively. Second harmonic generation (SHG) effect measurements have shown that their phase-matched SHG signals are 0.17, 0.20 and 0.28 times of KDP. Thermal stability analyses, optical property measurements and theoretical studies of them were also performed.
研究领域:
材料科学
·
晶体学
·
光学
✓ 已验证
DOI
高影响因子
CRYSTENGCOMM
·
2021
·Vol. 23
·期 37
·6518-6525
·
IF 3.545
Qi-Ming Qiu,Guo-Yu Yang
Three new mixed-alkaline-metal borates, namely KNa8[Li@B12O18(OH)6](CO3)2 (1), Cs10[Li@B12O20(OH)2]2·6H2O (2) and Cs5[Li@B12O20(OH)2]·3H2O (3), have been synthesized under hydro/solvothermal conditions. Compound 1 is a borate carbonate with the isolated [Li@B12O18(OH)6]5− clusters and interesting layers formed by Na+ and CO32− ions, forming a 2D supramolecular structure with a 3,6-connecting binodal system. After changing the synthetic conditions, the isolated [Li@B12O18(OH)6]5− clusters are successfully extended to the layers in 2 and 3 by condensation reactions with the elimination of water molecules between oxoboron clusters. Each new fundamental building block [Li@B12O22(OH)2]9− in 2 and 3 connects with four neighboring units to form a 2D layer via B–O–B bonds for the first time, and 14-membered rings are also observed. Such a layer structure is first observed in dodecaborates. Since compound 3 crystallizes in the non-centrosymmetric space group, the second harmonic generation measurement and the dipole moments calculation have been carried out.
研究领域:
无机化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2024
·
IF 3.2
Shu Li,Zhanmin Cao,Zhongnan Guo,Wenxia Yuan,Fan Sun,Hongmei Wang
This article reports a new perovskite compound Ca 6 Sb 2 O 11 . The X-ray powder diffraction technique was used to analyze its crystal structure. The results show that Ca 6 Sb 2 O 11 has a tetragonal structure with the I 4/ m space group, and the lattice parameters are a = b = 5.658 (1) Å, c = 7.984 (1) Å, α = β = γ = 90°. It exhibits a typical A 4 B' 2 B″ 2 X 12- x anoxic multi-perovskite structure with rock-salt ordering of the B-site cations. The compound's chemical composition and valence states were characterized through scanning electron microscopy-energy dispersion spectrum (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The presence of oxygen vacancies was confirmed by electron paramagnetic resonance (EPR) spectroscopy. A chemical and structure transition temperature and the full melting temperature of Ca 6 Sb 2 O 11 were measured, with values of 1515 ± 3 K and 1720 ± 3 K, respectively. The density functional theory (DFT)-electron structure calculation results show that Ca 6 Sb 2 O 11 is an indirect wide-band gap (∼4.47 eV) semiconductor material , which agrees well with the experimental value (∼4.38 eV) obtained through diffuse reflection spectroscopy (DRS). Moreover, the top of the valence band and bottom of the conduction band are mainly contributed to by O-2p and Ca-3d states, respectively.
研究领域:
材料科学
·
固体化学
·
计算物理
✓ 已验证
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2023
·
IF 3.3
Yue-Ling Sun,Gang-Xiang Liu,Yi-Lei Lv,Liang Ma,Wen-Dong Yao,Ru-Ling Tang
Phosphate crystals are valuable materials according to their diverse structures and physical and chemistry properties. A zinc orthophosphate, (NH 4 ) 3 (H 3 O)Zn 4 (PO 4 ) 4 , has been obtained via hydrothermal route. It was crystallized in hexagonal space group P 6 3 , featuring a three-dimensional (3D) [Zn(PO 4 )] – anion network built by corner-sharing connected ZnO 4 and PO 4 tetrahedra. The NH 4 + and H 3 O + units are located in the six-member cavities of the framework as the balanced cations. (NH 4 ) 3 (H 3 O)Zn 4 (PO 4 ) 4 exhibits a moderate and phase matchable second harmonic generation effect (SHG) about 1.4 times of KH 2 PO 4 (KDP), which is the strongest in zinc orthophosphates. Besides structural features, optical properties measurements and theoretical analyses of (NH 4 ) 3 (H 3 O)Zn 4 (PO 4 ) 4 were performed.
研究领域:
材料科学
·
光学
·
晶体学
·
化学
✓ 已验证
DOI
高影响因子
ZEITSCHRIFT FUR KRISTALLOGRAPHIE-NEW CRYSTAL STRUCTURES
·
2023
·Vol. 238
·期 4
·799-800
·
IF 0.3
Yu-Pei Xia
C 4 H 13 Cl 2 N 5 , monoclinic, P 2 1 (no. 4), a = 7.1868(6) Å, b = 5.8408(4) Å, c = 12.6534(11) Å, β =
105.134
(
2
)
∘
, V = 512.73(7) Å 3 , Z = 2, R
gt ( F ) = 0.0354, wR
ref ( F
2 ) = 0.0961, T = 298 K.
研究领域:
化学晶体学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2020
·
IF 4.825
Huimin Song,Naizheng Wang,Wang Liu,Jingcheng Feng,Jun Shen,Wei Dai,Zheshuai Lin,Jiyong Yao,Guochun Zhang
A gadolinium-rich borate Gd17.33(BO3)4(B2O5)2O16 was successfully grown by the high-temperature solution method using the Rb2O–B2O3 flux. The crystal crystallizes in centrosymmetric space group C2/m with lattice constants a = 18.4300(2) Å, b = 3.7400(4) Å, c = 14.2047(16) Å, and β = 119.8550(12)°. Two different honeycomb-like [GdO] layers alternately arrange in the order ABAB forming the three-dimensional framework, in which the isolated [B2O5] and [BO3] units fill in channels of the 12-membered and 10-membered [GdO] polyhedral rings, respectively. The UV cutoff edge of Gd17.33(BO3)4(B2O5)2O16 is less than 240 nm. The maximum −ΔSm,max is 26.53 J kg–1 K–1 or 174.70 mJ cm–3 K–1 (T = 4.4 K and ΔH = 7 T) as investigated by the isothermal magnetization method.
研究领域:
材料科学
·
固体物理学
·
晶体学
✓ 已验证
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2021
·
IF 3.498
Ce Tao,Jianqiang Li,Rukang Li
A new series of rare earth bismuth silicates has been synthesized by flux method and solid state reaction . LnBiSiO 5 (Ln = Ce, Tb) crystallizes in a triclinic space group P -1 with cell parameters a = 5.6763(2) Å, α = 105.591(3)° b = 6.7922(3) Å, β = 110.551(3)° c = 6.9593(2) Å, γ = 99.733(3)°, Z = 2. They exhibit a novel three-dimensional structure consisting of zig-zag chains of edge-sharing Ce/TbO 8 polyhedra that are further linked by SiO 4 units and Bi 2 O 8 clusters. The optical band gap (E g ) of TbBiSiO 5 was estimated to be 3.84 eV from UV–Vis-IR diffuse reflectance spectra. Photoluminescence measurements suggest that due to the cooperative interaction of Bi and Tb the excitation bands monitored at 544 nm are shifted towards longer wavelength which may favor commercial UV diode excitation. The magnetic measurements show that TbBiSiO 5 exhibits paramagnetic behavior without magnetic transitions down to 1.8 K.
研究领域:
材料科学
·
固体化学
·
光学材料
·
磁性材料
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Zhi-Hui Shi,Mei Yang,Wen-Dong Yao,Wenlong Liu,Sheng-Ping Guo
Two chalcogenophosphates, SnPS2.86Se0.14 (1) and SnPSe3 (2), are isostructural and crystallize in the monoclinic noncentrosymmetric space group Pn. Their three-dimensional (3D) structures are constructed by [Sn(1)Q8] hendecahedra and [Sn(2)Q8] dodecahedra by sharing Q vertices and edges, leaving cavities for isolated [P2Q6] (Q = S/Se, Se) dimers. A second-harmonic-generation (SHG) measurement indicates that 1 is phase-matchable with a response of approximately 1.2 × AgGaS2 (AGS), which is verified by the theoretical calculation result. The powder sample of 1 exhibits a high laser-induced damage threshold of 3.9 × AGS. For comparison, the known SnPS3 (3) was also synthesized and evaluated using the same method. The chemical composition–NLO performance relationship of 1–3 is also discussed. Dipole moment calculation results suggest that [SnQ8] polyhedra make the main contribution to their excellent nonlinear optical (NLO) performance.
研究领域:
材料科学
·
非线性光学
·
晶体学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）