Prismatic crystal field stabilized divalent rare-earth chalcogenide RE^IIB^II₆C^III₆Q^VI₁₆ with bifunctionality

The Innovation Materials, Journal Year: 2025, Volume and Issue: unknown, P. 100118 - 100118

Published: Jan. 1, 2025

<p>Divalent rare-earth (RE²⁺) compounds with unique electronic configurations have been known for more than 100 years, and many efforts done, but the synthesis of inorganic RE²⁺ chalcogenides is still a challenge due to chemical instability RE²⁺. Herein, nine new RE^IIB^II₆C^III₆Q^VI₁₆ (RE^II = La, Ce, Pr, Yb; B^II Mg, Mn; C^III Al, Ga; Q^VI S, Se) rationally designed in an octahedra tetrahedra composed flexible framework, fabricated experiment. In compounds, stabilized by prismatic crystal field, rather common octahedral field. The especially sulfides, exhibit significant luminescence properties wide visible light emission bands under excitation ultraviolet source. Meanwhile, representative LaMg₆Ga₆Se₁₆ exhibits strong nonlinear optical (NLO) response 1.5 × AgGaS₂ (AGS), high laser-induced damage threshold (LIDT) 3 AGS. results demonstrate that are bifunctional enriching diversity RE materials, opening avenue design functional materials based on stable anionic frameworks.</p>

Language: Английский

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New Ways to Discover Novel Nonlinear Optical Materials: Scaling Machine Learning with Chemical Descriptors Information

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 4, 2025

Abstract The efficient experimental exploration of innovative nonlinear optical materials has long been a challenging task due to the vast chemical space and lack suitable theoretical prediction frameworks. Herein, novel design paradigm is proposed accelerate discovery with strong second harmonic generation intensity. This challenge addressed through several key technologies. 1) A high‐precision machine learning model on maximum dataset. 2) Descriptors information paves way systematically offer valuable insights for designing structures. 3) flexible fast construction method proposed. Accordingly, crystal successfully synthesized constructed “machine knowledge” framework. compound exhibits stronger second‐harmonic response wider transmission range. work introduces concepts provides into or other functional materials.

Language: Английский

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One-Dimensional Perovskite RbGeI₃ with Large Optical Anisotropy

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

Published: Feb. 12, 2025

Inorganic halide perovskites have been regarded as potential candidates for nonlinear optical (NLO) materials due to their large bandgaps and second-harmonic generation (SHG) effects. If these crystals exhibit anisotropy, birefringent phase-matching ability will undergo enhancement. In this study, a one-dimensional (1D) perovskite, RbGeI3, was experimentally synthesized. Its [GeI3]∞1 double chains are parallelly arranged, resulting in structural anisotropy with birefringence of 0.122@1064 nm, the largest one reported NLO-active inorganic perovskites, determined from first-principles calculations. Furthermore, comprehensive characterization involving Raman spectroscopy, absorption spectrum, powder SHG measurement conducted assess its suitability NLO applications.

Language: Английский

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Impact of Microstructural Units Configuration and Arrangement on Phase-Matching in Nonlinear Optical KGa₅Se₈ Crystals

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: 17(9), P. 14250 - 14256

Published: Feb. 24, 2025

Achieving phase-matching (PM) behavior, which is typically derived from sufficient birefringence (Δn), crucial for maximizing the nonlinear optics (NLO) laser power output. Δn largely attributed to configuration and arrangement of microstructural units, phase transitions will significantly alter stacking method structural units. In this study, we successfully synthesized two diamond-like isomers α-KGa5Se8 (P21, 1) β-KGa5Se8 (P1, 2), consist open-honeycomb-like anionic frameworks interspersed with embedded K+ cations. Importantly, our analysis frequency doubling experiment data revealed a significant finding at wavelength 1910 nm: α-phase lacks PM capability, whereas β-phase exhibits behavior. Notably, through computational analysis, distinct primarily stems different arrangements tetrahedral units within phases. Specifically, polarizability anisotropy in 3.7 times that α-KGa5Se8. This uniform packing improves index 0.015 (α-phase) 0.023 (β-phase). Furthermore, not only demonstrates robust second-harmonic generation (SHG) response (2.1 × AgGaS2 @1910 nm) but also possesses wide band gap 2.56 eV, surpassing 2.33 eV threshold corresponds energy doubly light using 1064 nm laser, characteristic often exceeding most selenides. work underscores importance achieving NLO materials.

Language: Английский

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Enhanced Birefringence and Excellent Thermal Stability in Two Tellurium(IV) Vanadates: KTeOVO₄ and Ca₂TeV₂O₉

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

Published: Feb. 25, 2025

Two tellurium(IV) vanadates, KTeOVO4 and Ca2TeV2O9, were synthesized by integrating Te4+ with lone-pair of electrons V5+ exhibiting the second-order Jahn–Teller effect (SOJT) active centers. Both compounds feature unique one-dimensional chain structures formed [TeO4] [VOx] polyhedra, resulting in notable birefringence values 0.162 0.128 at 546 nm, respectively, higher than those commonly used materials like α-BaB2O4 (0.116@1064 nm) LiNbO3 (0.074@1440 nm). Additionally, they demonstrate excellent thermal stability (up to 500 700 °C) broad transparency ranges (0.39–10.00 μm 0.53–10.68 μm), enabling potential applications near- mid-infrared optical devices. Structural theoretical analyses reveal that enhanced arises from synergistic effects anisotropic polarizability

Language: Английский

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Size effect of cations in the A2B3O4F3 family: Based on the new member Cs2B3O4F3

Materials Today Chemistry, Journal Year: 2025, Volume and Issue: 45, P. 102623 - 102623

Published: March 6, 2025

Language: Английский

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Regulation of Refractive Index by Halogens in Two-Dimensional Layered Methylsulfonate Halides

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

Published: March 6, 2025

Herein, a series of unprecedented alkaline earth metal methylsulfonate halides, M(SO3CH3)X·nH2O (M = Sr, Ba; X Cl, Br, I; n 2, 4), and Ba2(SO3CH3)3I·4H2O were synthesized. They all feature two-dimensional (2D) layered structures with halogen elements inserted between the 2D layers constructed by ions [SO3CH3] groups, which are suitable for exploring influence halogens on their refractive index. The indexes both parallel (almost) perpendicular to calculated through theoretical calculations. We found that nonpolar exhibited different enhancement in two directions. result may guide regulating birefringence properties such crystal materials. Besides, ultraviolet (UV) cutoff edge Sr(SO3CH3)Cl·4H2O Ba(SO3CH3)Cl·4H2O can reach 183 184 nm, respectively, indicating potential application deep-UV region.

Language: Английский

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Tuning Birefringence in Supramolecular Mg-PDA Frameworks: Modulating Bonding and Layer Connectivity

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

Published: March 21, 2025

Herein, we prepared two novel hydrogen-bonded supramolecular frameworks within the Mg-pyridine dicarboxylic acid (Mg-PDA) system: [Mg(H2O)6][(C7H4NO4)·H2O]2 (1) and Mg(C7H3NO4)(H2O)2 (2). In compound 1, 2D [(C7H4NO4)·H2O]∞– anionic layer is formed by O/N–H···O hydrogen bonding connecting (C7H4NO4)− anions with free water molecules. contrast, [Mg(C7H3NO4)(H2O)2]∞ neutral in 2 connected Mg–O/N coordination bonds, which promote coplanar arrangement of π-conjugated six-membered pyridine rings. This structural enhances disparity between in-plane out-of-plane interactions [Mg(C7H3NO4)(H2O)2] layer. Consequently, both experimental data theoretical calculations indicate that shows strong optical anisotropy, giant birefringence (Δn = 0.44 @ 546 nm) surpassing 1 0.34 exceeding commercially available α-BaB2O4 0.122 nm). More importantly, combination their short-wave UV cutoff edges (279 nm for 273 2), features most promising birefringent properties among all Mg-containing crystals.

Language: Английский

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Polar [NH(CH₂SO₃)₂]²⁻ Dimers Enable the First Promising Iminodimethanesulfonate with Nonlinear Optical Properties and Wide UV Transparency

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Comprehensive Summary Non‐π‐conjugated groups have recently emerged as excellent fundamental building blocks (FBUs) for UV nonlinear optical (NLO) crystals, due to their ability achieve wide transparency. However, generally high crystallographic symmetry often results in limited anisotropy, making few resultant crystals phase‐matchable the wavelength range. In this work, we introduce polar [NH(CH 2 SO 3 ) ] 2− dimer a novel non‐π‐conjugated FBU, and synthesize first NLO iminodimethanesulfonate crystal, namely Cs NH(CH ·H O. Experimental demonstrate that crystal exhibits second‐harmonic generation (SHG) responses with 0.8 times of KDP, moderate birefringence 0.044@550 nm, broad transparency (< 200 nm), enabling SHG at key 266 nm. First‐principles calculations confirm dimers contribute properties This work highlights an NLO‐active FBU exploring high‐performance crystals.

Language: Английский

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Blue-Light-Excitable Yellow Emissive One-Dimensional Hybrid Copper(I) Iodide for White-Light-Emitting Diode and Methanol Sensing Application

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

Published: April 4, 2025

Copper(I) halides are promising candidates for advanced optoelectronics, such as white-light-emitting diodes (WLEDs), scintillators, and photodetectors. Designing synthesizing low-dimensional hybrid copper with blue-light excitation remains an enormous challenge. Herein, we have prepared two one-dimensional (1D) Cu(I)-based metal iodides, namely, (C6H7N)CuI (C6H8N)CuI2 single crystals, by deliberately adjusting the ratio of reactants 4-methylpyridine (4-MePy) CuI. crystals nonluminous, while exhibit unusual yellow emission a broad band in range 260-500 nm Furthermore, prototypical WLED is fabricated combining commercial 430 blue chip phosphor, which exhibits correlated color temperature (CCT) 5645 K CIE coordinate (0.329, 0.334), thus demonstrating potential application white lighting. Remarkably, emit red fluorescence upon adsorption methanol but fail all other alcohols. Notably, initial luminescence can be recovered volatilization from achieving reversible photoluminescence switching. This work not only presents important reference blue-light-excitable iodide phosphor WLEDs also provides intriguing sensor detection methanol.

Language: Английский

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