Nonbonding Electron Inversion‐Driven Structural Engineering: Synergistic Enhancement of Linear and Nonlinear Optical Properties DOI

Jia‐Xiang Zhang,

Shenghua Zhou,

Xin‐Tao Wu

et al.

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

Abstract The simultaneous optimization of large birefringence (Δn, a linear optical property) and strong second‐harmonic generation (SHG, nonlinear (NLO) in single crystal remains significant challenge due to the inherently distinct structural requirements for these properties. Although nonbonding electrons have been extensively studied oxides chalcogenides, research has predominantly focused on their role along polar axes, leaving influence axes tetrahedral stacking largely unexplored. Herein, we propose electron‐inversion strategy overcome phase‐matching limitations defect diamond‐like structures. By incorporating T2‐[Ga 4 S 10 ] supertetrahedral motifs, successfully synthesized [Ba Cl 2 ][CdGa (space group: I ), which exhibits 219% enhancement Δn compared nonphase‐matching parent structure Cd GaS . weakly bound electrons, governed by atomic potentials, demonstrate SHG responses under fields. compound not only achieves broad transmission range (0.28–18.6 µm) high laser‐induced damage threshold (40.1 × AgGaS ) but also optimally balances wide bandgap ( E g = 3.58 eV) response (1.4 representing one best‐performing Cd‐based materials date. This work introduces first design based electron‐driven structure–property relationships, providing critical insights rational high‐performance NLO materials.

Language: Английский

Rational Design and Controlled Synthesis of High-Performance Inorganic Short-Wave UV Nonlinear Optical Materials DOI

Xuehua Dong,

Ling Huang, Guohong Zou

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 12, 2024

ConspectusThe invention of the laser marked a milestone in modern science and technology. Inorganic second-order nonlinear optical (NLO) crystals, with their unique frequency conversion capabilities, play critical role extending wavelength ranges. These materials are indispensable science, information transmission, other fields such as industrial Internet. As Moore's Law drives demand for shorter wavelengths higher-precision sources, development high-performance short-wave ultraviolet (UV) (<300 nm) NLO UV solid-state lasers has become increasingly important. While researchers have synthesized variety discovery largely relied on trial-and-error approaches, which not only time-consuming but also serendipitous rather than based rational design principles. Moreover, complexity designing these is compounded by need to meet several strict functional criteria, including short cutoff edge, strong second-harmonic generation (SHG) effect, moderate birefringence, all hinder efficient synthesis. The controlled synthesis therefore, remains significant scientific challenge.In this Account, we propose three-step strategy address challenge: (1) Rational screening highly polar groups, particularly new NLO-active groups novel bonding characteristics (π-localized distorted [O

Language: Английский

Citations

25
Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units DOI
Bo Zhang,

Mao‐Yin Ran,

Xin‐Tao Wu

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 517, P. 216053 - 216053

Published: July 3, 2024

Language: Английский

Citations

21
[(C5H6N2)2H](Sb4F13): A polyfluoroantimonite with strong second harmonic generation effect DOI Creative Commons

Jia-Hang Wu,

Chun‐Li Hu, Yafeng Li

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(21), P. 8071 - 8079

Published: Jan. 1, 2024

A universal synthesis method for polyfluoroantimonites has been developed. Polar [(C 5 H 6 N 2 ) H](Sb 4 F 13 was achieved by polyfluoroantimonite strategy. It features a strong SHG effect, large birefringence and high LIDT value.

Language: Английский

Citations

16
Looking Back the Nonlinear Optical Crystals in a Functionalized Unit's Perspective DOI Creative Commons
Miriding Mutailipu, Junjie Li, Shilie Pan

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 15, 2024

Abstract Nonlinear optics, signifying a revolutionary paradigm change within the realm of has ushered in transformative era by employing nonlinear optical crystals to manipulate and harness laser power for at least six decades. The most exciting aspects (NLO)crystal is repercussions bonding over extended functionalized units external force how slight alterations atomic scale can result huge changes macroscopic properties. However, date, precisely controlling unit its potential induce directed property is, yet, not fully realized. Here, NLO are explored prospected from viewpoint unit, with an emphasis on application material design control regulate key properties start regulating their functions. An introduction anionic group theory started here, which considers functional be primary, then turns discussion modification through emerging strategies this facilitates new materials. Additional breakthroughs rational strategy functionalize groups covered, including integration, preferential arrangement induction, microcosmic performance maximization as well supports these materials discovery theoretical method. Beyond gratifying achievements made, some future perspectives move step forward finally provided.

Language: Английский

Citations

13
Crystal clear: unveiling giant birefringence in organic–inorganic cocrystals DOI Creative Commons
Yang Li, Kang Min Ok

Chemical Science, Journal Year: 2024, Volume and Issue: 15(26), P. 10193 - 10199

Published: Jan. 1, 2024

[LiNO 3 ·H 2 O· o -C 5 H NO]· NO and [Mg(NO ) ·6H O]·( NO) , with giant birefringence, large bandgaps, good growth habits, were designed using a cocrystal strategy.

Language: Английский

Citations

12
Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals DOI
Yang Li, Kang Min Ok

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 26, 2024

Abstract Birefringent crystals have essential applications in optical communication areas. Low‐dimensional structures with inherited structural anisotropy are potential systems for investigating birefringent materials large birefringence. In this work, the zero‐dimensional (0D) [( p ‐C 5 H NO) 2 ZnCl ] ( 1 ) and [ 6 NO] [ZnCl 4 were obtained by introducing π‐conjugated NO (4HP) into three‐dimensional (3D) . Remarkably, exhibits a giant birefringence of 0.482@546 nm, which is largest among Zn‐based ultraviolet (UV) compounds 160 times that According to theoretical calculation analyses, polarizability, high spatial density, ideal distribution [(4HP) 0 cluster, low dimension result dramatically increased compared This work will provide valid route accelerating design synthesis excellent low‐dimensional systems.

Language: Английский

Citations

9
Halogen Bond Unlocks Ultra‐High Birefringence DOI
Jin Chen, Mingsheng Xu,

Huai‐Yu Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 10, 2024

Anisotropy is crucial for birefringence (Δn) in optical materials, but optimizing it remains a formidable challenge (Δn >0.3). Supramolecular frameworks incorporating π-conjugated components are promising achieving enhanced because of their structural diversity and inherent anisotropy. Herein, we first synthesized (C

Language: Английский

Citations

8
Research progress in optical materials with cationic organic planar π-conjugated groups containing CN bonds DOI

Hangwei Jia,

Xueling Hou, Shilie Pan

et al.

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

Published: Jan. 1, 2024

The calculated polarizability anisotropy, hyperpolarizability and HOMO–LUMO gap of optically active groups.

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
Toward Strong UV–Vis–NIR Second-Harmonic Generation by Dimensionality Engineering of Zinc Thiocyanates DOI
Haijun Zhang, Xingxing Jiang, Yiran Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

The precise modulation of the spatial orientations and connection modes primitives is vital for certain critically important optical functions nonlinear (NLO) materials (specifically, second-harmonic generation (SHG) bandgap); however, we are yet to achieve a sufficient level control designed construction efficient broadband NLO materials. Exploiting changes in microscopic polarization that may result from dimensional increase, propose herein zero-dimensional (0D)-to-three-dimensional (3D) dimensionality-increase strategy realize strong SHG responses first time. novel 3D pseudo diamond-like Zn(SCN)2 has been synthesized by removing SHG-inactive [NH4]+ counter cations H2O molecules located between adjacent discrete [Zn(SCN)4] building blocks within 0D (NH4)2Zn(SCN)4·3H2O. 0D-to-3D dimensionality engineering, proceeding (NH4)2Zn(SCN)4·3H2O Zn(SCN)2, results significantly enhanced activity (8 × KH2PO4 @ 1064 nm, 4.18 eV bandgap former c.f. 2 β-BaB2O4 380 30 KTiOPO4 2100 4.78 latter) UV NIR regions (SHG@300–1050 nm). Theoretical calculations crystal structure analyses reveal coordination-bond-connected responsible its giant responses.

Language: Английский

Citations

6