Inorganic Chemistry Frontiers
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2022
·Vol. 9
·期 23
·6067-6074
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IF 7.779
Man Zhang,Bingbing Zhang,Daqing Yang,Ying Wang
A new birefringent crystal [C(NH2)3]2S2O8 was obtained by combining the π-conjugated [C(NH2)3] cation and the [S2O8] groups with localized O–O π-bonds. Optical measurements show that the UV cutoff wavelength of [C(NH2)3]2S2O8 is 222 nm, and its birefringence is 0.102 at 546 nm. The calculated results show that its large birefringence is attributed to the synergistic effect of the [C(NH2)3] and [S2O8] units, which is the first case among known birefringent crystals. These results provide new insights into the design of superior birefringent materials.
研究领域:
材料科学
·
光学
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DOI
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INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Zhiyong Bai,Lehui Liu,Zhoubin Lin,Kang Min Ok
A novel guanidinium-templated ultraviolet (UV) nonlinear optical zinc carbonate crystal, [C(NH2)3]2Zn(CO3)2 (GZCO), has been synthesized in a closed system at low temperatures. GZCO crystallizing in the tetragonal noncentrosymmetric nonpolar space group, P41212 exhibits a three-dimensional anionic framework constructed by interconnected [Zn6C6O32] 12-membered ring channels with inorganic CO3 triangles and ZnO4 tetrahedra. Notably, the anhydrous GZCO shows a very high thermal stability among guanidine-based hybrid NLO materials benefiting from the confinement effect of the organic cations within inorganic channels. The UV–visible transmittance spectrum reveals that GZCO has a short UV cutoff edge of 210 nm, corresponding to the large band gap of 5.9 eV. GZCO exhibits a mild second-harmonic generation efficiency of 0.5 × KH2PO4 with type-I phase-matching behavior.
研究领域:
材料科学
·
光学
·
化学
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DOI
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INORGANIC CHEMISTRY
·
2026
·
IF 4.7
Hangwei Jia,Yaqi Jin,Junwei Feng,Bailin Chen,Feng Yu,Xueling Hou
Guanidine units have garnered significant attention in the study of ultraviolet (UV) nonlinear optical (NLO) materials due to their excellent microscopic optical properties, making them ideal systems for developing novel optical devices. A novel guanidinium-templated UV NLO crystal, [C(NH2)3]SbCl4 (GSC), was successfully synthesized via an aqueous solution method. GSC crystallizes in the orthorhombic chiral space group P212121, featuring a seesaw shaped [SbCl4]− anion. Remarkably, GSC exhibits a moderate second harmonic generation (SHG) response of 1.1 × KDP at 1064 nm and a large refractive index difference of 0.2 at 546 nm. This NLO effect originates from the synergistic interaction between the [C(NH2)3]+ unit and the stereochemically active [SbCl4]− unit. This work provides a candidate for the guanidine family of NLO materials.
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产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CHEMISTRY
·
2025
·
IF 5.5
Shaohua Liu,Xiaoqin Ma,Xifa Long,Yun Yang
Comprehensive Summary Birefringent crystals exhibit significant advantages in the field of polarization state modulation due to their unique optical anisotropy properties. The property optimization between bandgap and birefringence depends on the crystal structure, which is always a key scientific problem in the field of functional crystal materials design. In this work, the fluorination-oriented strategy was applied to the design of crystals with large birefringence and deep ultraviolet (DUV) cutoff edges. By introducing the fluorinated [SiF 6 ] octahedron, the arrangement orientation of the π-conjugated [C(NH 2 ) 3 ] groups was accurately regulated, thereby achieving the design and preparation of a new crystal [C(NH 2 ) 3 ] 2 SiF 6 with a large bandgap (6.34 eV) and large birefringence (0.16 @546 nm). In addition, [C(NH 2 ) 3 ] 2 SiF 6 (GSF) can obtain large-sized crystals through a simple water solution evaporation method, and it has unique advantages such as low cost and easy growth. The synergistic mechanism between the core factors of significant birefringence and wide bandgap in [C(NH 2 ) 3 ] 2 SiF 6 was revealed through experimental characterization and theoretical calculation. This work provides promising candidates with exceptional properties for DUV applications.
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ACS Applied Optical Materials
·
2025
·
IF 3.8
Huan Zhou,Meng Cheng,Zhihua Yang,Shilie Pan
Birefringent materials are crucial optical materials that enable the control of polarized light in optical technologies, yet achieving high birefringence in systems dominated by non-π-conjugated units in the deep-ultraviolet (UV) region remains a significant challenge. Herein, a birefringent material, [C(NH2)3]2PO3(OH), was successfully synthesized by integrating π-conjugated [C(NH2)3] units and heteroleptic tetrahedra [PO3(OH)]. The short UV cutoff edge (<200 nm) and large birefringence (0.086 @ 546 nm) make [C(NH2)3]2PO3(OH) a potential deep-UV birefringent crystal. This study provides the experience for the design of deep-UV optical crystals.
研究领域:
材料科学
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光学
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无机化学
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晶体工程
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产品关联
DOI
高影响因子
Science China-Materials
·
2021
·Vol. 64
·期 8
·2008-2016
·
IF 8.273
Wen Xin,Lin Chensheng,Luo Min,Fan Huixin,Chen Kaichuang,Ye Ning
[PO 4 ] 3− possesses small microscopic second-order susceptibility and polarizability anisotropy, which inherently result in weak second-harmonic generation (SHG) and small birefringence. Herein, a new noncentrosymmetric phosphate, [C(NH 2 ) 3 ] 3 PO 4 ·2H 2 O, was successfully designed and synthesized by a solution evaporation method. [C(NH 2 ) 3 ] 3 PO 4 ·2H 2 O without metal ions is composed of planar conjugated guanidine cations and PO 4 tetrahedrons, which are connected by hydrogen bonds, forming a three-dimensional network. Physical property measurements indicate that the title compound displays an SHG response of 1.5 × KH 2 PO 4 (KDP) and a larger birefringence (0.055@546.1 nm) compared with most reported ultraviolet nonlinear optical phosphates. Furthermore, first-principles calculations reveal that the π-conjugated planar [C(NH 2 ) 3 ] + cations and [PO 4 ] 3− groups are responsible for its excellent linear and NLO properties.
研究领域:
材料科学
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光学工程
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无机化学
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晶体工程
·
非线性光学
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DOI
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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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CRYSTAL GROWTH & DESIGN
·
2024
·
IF 3.2
Wenyao Zhang,Zichen Li,Xudong Leng,Qun Jing,Qiao Wen
The development of efficient methods for producing novel birefringent materials has become a significant and urgent undertaking. Herein, we propose to use organic units as a structural guide to obtain organic–inorganic hybrid structures, where oxyfluoride units are used to optimize the arrangement of organic motifs, resulting in an enhanced optical anisotropy of the structure. Two novel C(NH2)3+-containing oxofluorovanadates, [C(NH2)3]3V2O4F5 (Gu3V2O4F5) and [C(NH2)2NHCH2COOH]2VOF5 (guanidinoacetic acid-VOF5, GA2VOF5) with dimensions up to 5 × 4 × 0.1 and 5 × 3 × 1 mm3, have been successfully designed and grown via facile reactions. Remarkably, Gu3V2O4F5 features an optimized two-dimensional (2D) van der Waals layer structure. It shows a birefringence of 0.35 at 546 nm (cal.); this is larger than most previously reported birefringences of C(NH2)3+-based organic–inorganic compounds. Additionally, it possesses an ultraviolet cutoff edge. GA2VOF5 is the first GA-containing oxofluorovanadate with a birefringences of 0.066 at 546 nm (cal.), which was verified experimentally. Theoretical calculations show that the remarkable birefringence observed in the title compounds primarily arises from the incorporation of π-conjugated units and [VOxF6–x] (x = 1 and 2) groups. Our study further confirms the effectiveness of structural optimization in the design and engineering of structural-driven functional materials.
研究领域:
材料科学
·
光学
·
化学
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DOI
高影响因子
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