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

C6N7(NH2)3·H3PO4: Strong Second Harmonic Generation and Giant Birefringence Benefiting from Amino Substitution Strategy DOI

Ruqing Wei,

Hongbo Huang, Daqing Yang

et al.

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: 12(35)

Published: Aug. 22, 2024

Abstract With the advancement of laser technology, searching for new nonlinear optics (NLO) active units is necessary designing NLO materials with excellent performance. In this study, an amino substitution strategy proposed to explore planar π‐conjugated groups as functional building (FBUs) and birefringent materials. Accordingly, a NLO‐active molecule melem C 6 N 7 (NH 2 ) 3 identified, which characterized by significant polarization anisotropies large hyperpolarizabilities. Subsequently, ·H PO 4 screened out successfully synthesized through simple aqueous method. The compound exhibits strong second harmonic generation (SHG) response 8.9 times that KDP birefringence 0.609 at 1064 nm. As far known, calculated largest among organic–inorganic hybrid crystals in originates from groups. theoretical computation supports (─NH effective synthesis SHG birefringence.

Language: Английский

Citations

5
l-Homoproline-Directed Synthesis of Organic–Inorganic Metal Iodides for Second Harmonic Generation DOI

Juan Cheng,

Gangji Yi,

Peiqi Qian

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(34), P. 15579 - 15583

Published: Aug. 15, 2024

Three organic–inorganic metal iodides, namely, (NH4)(l-hp)ZnI3 (1), [Cd(l-hp)4]Cd3I8 (2), and (l-Hhp)(l-hp)PbI3 (3), have been synthesized using l-homoproline (l-hp) as the structure-directing agent. These compounds feature different noncentrosymmetric structures optical properties. In particular, compound 3 shows a large second-harmonic-generation response of 3.4 times that KH2PO4. Density functional theory calculations were performed to gain insight into its structure–property relationship.

Language: Английский

Citations

4
Reconstructing Nearly Isotropic Microstructures to Construct One-dimensional Framework Causing the Record Birefringence in Thiophosphates DOI Creative Commons

Lin‐Tao Jiang,

Xiao‐Ming Jiang, Yuhang Fan

et al.

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

Published: Jan. 1, 2024

Novel birefringent materials, α-Rb 2 InP S 7 , β-Rb and Cs were reconstructed from the nearly isotropic basic building units displayed largest birefringence among all known thiophosphates.

Language: Английский

Citations

4
Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs DOI

Jiarong Lv,

Gangji Yi,

Xuan Zou

et al.

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

Published: Dec. 3, 2024

Birefringent crystals with significant optical anisotropy have played a pivotal role in laser technology and scientific research by modulating controlling light polarization. In this study, we successfully synthesized three new birefringent materials mixed-valence antimony, namely, KSb3O6, RbSb3O6, α-Sb2O4, through the introduction of Sb3+ stereochemically active lone pairs (SCALP) to total oxygen system using high-temperature solution method. To best our knowledge, K/RbSb3O6 represents first alkali metal Sb-based oxide. Interestingly, despite their similar sandwich structure, these exhibit vastly different levels birefringence (almost 10 times difference). It is worth noting that α-Sb2O4 demonstrates largest experimental (0.201 at 546 nm) among non-π-conjugated oxides date, which can be attributed synergistic effect SCALP group distortion arrangement. These findings hold valuable implications for guiding future efforts designing synthesizing large materials.

Language: Английский

Citations

4
Unveiling Charge Dependent Law to Enhance Birefringence in 2‐Aminopyrimidine Family DOI
Muhammad Arif, Xu Liu, Zi‐Jian Li

et al.

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

Published: Dec. 16, 2024

Abstract Salts and co‐crystals composed of planar π ‐conjugated functional units represent a fascinating class materials, featuring both enlarged birefringence strong SHG effect. Herein, the optical properties (C 4 H 7 N 3 ) 2+ unit within 2‐aminopyrimidine (2‐AP) family are investigated for first time. Furthermore, twelve novel compounds successfully synthesized by applying four different strategies. In these strategies, , 6 + 5 introduced into crystal structure, solely in combination, to analyze alteration birefringence. Remarkably, rule with < ), stating that an increase net charge over leads reduced birefringence, is discovered. Consequently, inclusion charge‐neutral structure along coplanar arrangement promising approach enhance D‐2 [(C )(H C O )] realizes Δn calc = 0.412 maximum family. Notably, A‐1 )(CF SO 2 ] B‐1 (IO (H O)] crystalize non‐centrosymmetric space groups, exhibiting efficiency ≈1.4 × KDP @ 1064 nm, shortest λ PM at 384 nm. This work provides new insight discovering birefringent non‐linear materials high performances wide chemical space.

Language: Английский

Citations

4
Halogen Bond Unlocks Ultra‐High Birefringence DOI
Jin Chen,

Miao‐Bin Xu,

Huai‐Yu Wu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(44)

Published: July 10, 2024

Abstract Anisotropy is crucial for birefringence (Δ n ) in optical materials, but optimizing it remains a formidable challenge >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 6 H NO 2 + Cl − ( NAC then constructed halogen‐bonded supramolecular framework I 4 INA by halogen aliovalent substitution with . The organic moieties protonated deprotonated nicotinic acid NA ), respectively. antiparallel arrangement birefringent‐active units leads to significant differences the bonding characteristics between interlayer intralayer domains. Moreover, [O⋅⋅⋅I ⋅⋅⋅N] bond 1D [I ] chain exhibits stronger interactions stricter directionality, resulting more pronounced in‐plane anisotropy intrachain interchain directions. Consequently, exceptional birefringent performance, value 0.778 at 550 nm, twice that (0.363 nm). This significantly exceeds those commercial crystals, such as CaCO 3 (0.172 546 nm), highest reported among ultraviolet crystals. work presents novel design strategy employs bonds connection sites modes units, opening new avenues developing high‐performance

Language: Английский

Citations

3
Zwitterionic Glycine-Based Antimony Fluorides with Exceptional Ultraviolet Nonlinear Optical Properties DOI
Yunseung Kuk, Zhiyong Bai, Yang Li

et al.

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

Published: Jan. 20, 2025

Language: Английский

Citations

0
Enhanced Birefringence and Excellent Thermal Stability in Two Tellurium(IV) Vanadates: KTeOVO4 and Ca2TeV2O9 DOI
T. Wang, Han Luo, Shunke Zhang

et al.

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

Citations

0
pH‐Dependent Switching Between Nonlinear‐Optical‐Active Nitrate‐Based Supramolecular Polymorphs DOI Open Access
Xia Qin, Xingxing Jiang,

Chunbo Jiang

et al.

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

Published: March 11, 2025

Tailored syntheses of non-centrosymmetric (NCS) second-order nonlinear optical (NLO) crystals, particularly those metastable NCS polymorphs, remain extremely challenging due to the complex interactions their constituent primitives. In this work, we report first successful synthesis a set three nitrate supramolecular polymorphs (C2H5N4)(NO3) (α-, β-, and γ-phases) by pH-modulation secondary-bond strategy, via assembly two types π-conjugated planar Solutions different pH result in differing orientation secondary bonds between [C2H5N4] [NO3] Secondary dominate packing primitives crystal lattices; varying these can afford or centrosymmetric with 2D α-phase irreversibly transformed β-phase solution appropriate pH. These display distinctly SHG responses birefringences, ascribed variation stacking hydrogen-bond layers resulting from environmental Supramolecular structures comparison theoretical studies confirm crucial role played adjacent rare polymorphs. This work paves way elucidating polymorph transition-mechanisms correlating NLO properties, thereby discloses new paradigm for development high-performance materials tailored properties.

Language: Английский

Citations

0
Inch‐sized K[NH2(CH2COO)2]: a High‐Performance UV Nonlinear Optical Crystal Enabled by Novel Flexible π‐Conjugated Building Units, [NH2(CH2COO)2]− DOI Open Access
Yujie Fan, Lingli Wu,

Chensheng Lin

et al.

Laser & Photonics Review, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Abstract High‐performance ultraviolet (UV) nonlinear optical (NLO) crystals must exhibit three critical properties: a large second‐harmonic generation (SHG) response, adequate birefringence, and short UV cutoff edge. However, these key characteristics are often interdependent challenging to achieve simultaneously within single crystal. In this study, novel non‐centrosymmetric compound, K[NH 2 (CH COO) ] is introduced, synthesized from the innovative flexible π‐conjugated group [NH − . Benefiting excellent microscopic properties of groups, despite suboptimal arrangement groups still demonstrates remarkable balance in its linear performance. This includes strong SHG response 3 times that KDP, suitable birefringence 0.088@1064 nm, edge at 208 nm. Emphatically, high‐quality, inch‐sized (up 60 × 46 30 mm ) successfully grown using water solution technique, paving way for practical applications promising material.

Language: Английский

Citations

0