[C3H7N6]3[B3O5(OH)2] and [C3H8N6]4[B12O19(OH)6]: Two Melamine Borates with Large Birefringence DOI
Yunfeng Deng, Chun‐Li Hu, Jiang‐Gao Mao

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 18, 2024

The π-conjugated [C3H6+xN6]x+ (x = 0–3) cations are good functional groups, which widely employed in the preparations of nonlinear optical (NLO) and birefringent materials due to their high hyperpolarizability anisotropy. In this paper, first melamine hydroxyborate [C3H7N6]3[B3O5(OH)2] (MelBO-I) was synthesized by boric acid melting method under molar ratio H3BO3:C3H6N6 1:1. MelBO-I (P21/c) exhibits a two-dimensional (2D) {[C3H7N6]3[B3O5(OH)2]}∞ layer composed [C3H7N6]+ [B3O5(OH)2]3– anions interconnected via hydrogen bonds. significant birefringence (Δn 0.286@546 nm). Under H3BO3/C3H6N6 3:1, [C3H8N6]4[B12O19(OH)6] (MelBO-II) isolated. MelBO-II (P21), highly polymerized [B12O19(OH)6]8– groups form 3D network through bonding, featuring 1D tunnels 8-membered 16-membered rings filled [C3H8N6]2+ cations. is noncentrosymmetric (NCS) bifunctional borate with moderate SHG response (0.4 × KDP) large 0.285@546 results indicate that incorporating into can effectively induce birefringence. A concentration promotes formation cluster facilitates transformation from CS NCS structure.

Language: Английский

Cationic Modification in Hybrid Iodates: A Pathway to Superior Performance DOI
Jingjing Zhao, Shu‐Fang Li,

Meng-Han Lv

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

The utilization of nonlinear optical (NLO) crystals plays a crucial role in the contemporary laser industry, and advancement novel NLO-active units is essential for exploration NLO materials. Two organic–inorganic hybrid iodates, designated as (C3N2H5)2Mo2O5(IO3)4·3H2O (1) (C3N2I2H3)2Mo2O5(IO3)4·4H2O (2) were synthesized via mild hydrothermal methods, exhibiting band gaps 3.75 3.00 eV, SHG response 1.3 3.5 times that KDP, birefringence 0.143 0.254@ 550 nm, respectively. property enhancement can be attributed to cationic modification strategy, corroborated by results theoretical calculations.

Language: Английский

Citations

4
Exploring New Horizons in Mid-to-Far Infrared Nonlinear Optical Crystals: The Significant Potential of Trigonal Pyramidal [TeS3]²⁻ Functional Units DOI Creative Commons
Bo Zhang, Shenghua Zhou, Bingxuan Li

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The [TeS 3 ] 2− unit with a SCALP disrupts tetrahedral symmetry, leading to the synthesis of Cu 10 Te 4 S 13 for first time. This material exhibits strong SHG (3.75 × AgGaS 2 ) and widest MFIR transparency (2.5–25 μm) reported NLO chalcogenides.

Language: Английский

Citations

2
Hg2(SeO3)(TeO3): A novel tellurite-selenite birefringent crystal achieved by assembling multiple functional groups DOI
Pengfei Li, Chun‐Li Hu, Jiang‐Gao Mao

et al.

Journal of Materials Chemistry C, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Hg 2 (SeO 3 )(TeO ), a new tellurite–selenite birefringent crystal, showcases broad transparency range, large birefringence, and high thermal stability, positioning it as promising material.

Language: Английский

Citations

2
The Directional Design of the Quasi‐Phase‐Matching Short‐Wave Ultraviolet Nonlinear Optical Crystal DOI
Hongyuan Sha,

Dongling Yang,

Yanran Shang

et al.

Laser & Photonics Review, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 13, 2024

Abstract Since the study of short‐wave ultraviolet nonlinear optical crystals based on quasi‐phase‐matching principle will effectively expand development field materials, it is urgent to achieve their directional design. Here, proposed and implemented account hexagonal wurtzite structure. Thus, LiRbSeO 4 crystal obtained with [SeO ] groups as main tetrahedra [LiO separation. It exhibits a wide transparency window (0.22–5.57 µm) an excellent effect (≈1.7 × KH 2 PO ), which originates from synergy distorted tetrahedral uniform arrangement. More importantly, confirmed be ferroelectric typical polarization‐electric hysteresis loop (a coercive 27.71 kV cm −1 , remanent polarization 8.60 µC −2 at 373 K). Its ferroelectricity further identified by domain engineering studies, involving piezoelectricity chirality. Besides, attributed ordered arrangement reversal atomic displacements. Therefore, promising candidate principle. This work also provides new horizon for design crystals.

Language: Английский

Citations

9
Fully Tricoordinated Assembly Unveils a Pioneering Nonlinear Optical Crystal (SbTeO3)(NO3) DOI Creative Commons
Haifeng Zhang, Chun‐Li Hu, Jiang‐Gao Mao

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Fully tricoordinated assembly yields the first tellurite-antimonite NLO crystal, (SbTeO 3 )(NO ), exhibiting well-balanced properties: a strong SHG effect (2.2 × KDP), short UV cutoff edge (253 nm) and moderate birefringence (0.081@546 nm).

Language: Английский

Citations

8
A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units DOI
Pengfei Li, Chun‐Li Hu, Jiang‐Gao Mao

et al.

Laser & Photonics Review, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 24, 2024

Abstract Phosphate crystals are known for their low birefringence, a result of the symmetrical tetrahedral structure PO 4 groups. Attempts to increase birefringence have traditionally involved incorporation highly anisotropic ions and Yet, majority modified phospates still exhibit value below 0.1, due counteracting effects elements within coordination. The present study has first time discovered novel birefringence‐active Hg I 2 II O 9 unit successfully constructed layered structure, which ingeniously prevents mutual cancellation effects. This synthesis (Te ) (HPO confirms effectiveness this strategy, yielding 0.444 at 546 nm, outperforms 99% phosphate surpasses that commercial counterparts like YVO (0.209@1064 nm) CaCO 3 (0.175@533 nm). Structural analysis PAWED calculations indicate significant is attributed synergistic interaction between (23.76%), HPO tetrahaedron (24.24%) TeO group (51.99%). breakthrough paves way phosphates meet demands modern technological advancements, expanding potential applications in field optics.

Language: Английский

Citations

7
Chemical Substitution‐Driven Design of a High‐Performance Noncentrosymmetric Bismuth Molybdenum Selenite DOI Creative Commons
Hieu Minh Ngo, Yunseung Kuk, Jihyun Lee

et al.

Advanced Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Abstract The hydrothermal synthesis and characterization of a novel bismuth molybdenum selenite material, Bi 2 F (MoO 3 ) (SeO ·H O, designed using chemical substitution‐based approach, is reported. This material represents the first example its kind in Bi–Mo–Se system, providing new insights into noncentrosymmetric (NCS) crystal engineering. compound exhibits outstanding nonlinear optical (NLO) properties, including second‐harmonic generation (SHG) efficiency 1.2 times that KTiOPO₄ birefringence 0.118 at 546.1 nm. Additionally, it demonstrates wide transparency range (0.36–10 µm), making promising candidate for advanced NLO applications. Structural computational analyses show remarkable SHG response driven by highly distorted MoO₆ octahedra, strong interatomic interactions within 1D chains, polarizable ⁺ SeO₃ groups. Furthermore, thermally stable after dehydration affinity occupying void space 5‐membered ring (5‐MR). These findings open avenues design NCS materials with enhanced functionalities, offering significant potential development solid‐state materials.

Language: Английский

Citations

1
Zero-Dimensional Oxyselenide Ba12[(Ga2OSe5)3(Si2O7)]: Enhanced Optical Anisotropy through Heteroanionic Engineering DOI

Yong‐Fang Shi,

Shenghua Zhou, Bo Zhang

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 11, 2025

The rational design of chalcogenides with exceptional optical properties remains a significant challenge. Here, we employ heteroanionic engineering to incorporate selenium into the celsian-type BaGa2Si2O8, synthesizing novel zero-dimensional oxyselenide, Ba12[(Ga2OSe5)3(Si2O7)]. It crystallizes in hexagonal space group P63/m and features isolated [Si2O7] [Ga2OSe5] clusters, balanced by Ba2+ cations. unit, reported for first time oxychalcogenides, marks structural breakthrough. compound exhibits wide bandgap (Eg = 3.14 eV), broad IR transmission (0.39-20.4 μm), high thermal stability (up 1100 K). Theoretical calculations reveal that 18-fold enhancement birefringence, increasing from 0.0038 0.068 at 1064 nm, compared its parent structure. This improvement is largely due role unit enhancing anisotropy. work highlights potential designing advanced birefringent materials, paving way functional crystals.

Language: Английский

Citations

1
From Pb6(HPO3)(H2PO3)Cl9 to Pb6(HPO3)2Br8(H2O)·H2O: Halogen Regulation to Achieve Inorganic Metal Phosphite Halide Nonlinear Optical Material with Unprecedented Pb-Centered Polyhedral Units DOI
Ru‐Ling Tang, Liang Ma,

Yi‐Lei Lv

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(29), P. 13197 - 13201

Published: July 8, 2024

Nonlinear optical (NLO) crystals are widely used in various fields. The introduction of lone-pair cations is regarded as an effective strategy to explore NLO crystals. In this work, two novel lead phosphite halides, centrosymmetric Pb

Language: Английский

Citations

5
Balanced IR Nonlinear Optical Performance Achieved by Cation–Anion Module Cosubstitution in V-Based Salt-Inclusion Oxychalcogenides DOI Creative Commons

Moshe Ran,

Shenghua Zhou, Bingxuan Li

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 3, 2024

Oxychalcogenides have become notable contenders for infrared nonlinear optical (IR NLO) applications because of their diverse heteroanionic functional motifs. However, while the main group elements are well-explored these motifs, transition been less studied and lack high-performance materials. To address this gap, we investigated a series noncentrosymmetric [Ba4(Ba6S)][(VOxS4–x)6] (space group: P63), first V-based salt-inclusion oxychalcogenides demonstrating phase-matched IR-NLO properties. We achieved by cation–anion module cosubstitution in centrosymmetric structure [Ba4(Ba6Cl2)][(VO4)6] P63/m). The novel features isolated [VOxS4–x]3– units, charge-balanced Ba2+ cations, one-dimensional cationic chain [Ba6S]10+ octahedral units. Moreover, [Ba4(Ba6S)][(VO3S)6] exhibits properties including high second-harmonic-generation intensity (1.33 × AgGaS2@2900 nm), substantial laser-induced damage threshold (7.65 AgGaS2), broad IR cutoff edge (up to 11.2 μm), significant birefringence phase matching (Δn = 0.073@2900 nm). Structural analysis DFT calculations demonstrate that configuration [VO3S]3– units enhances NLO increases structural anisotropy. Our findings suggest promising class highlight as an effective approach creating crystals.

Language: Английский

Citations

5