Looking Back the Nonlinear Optical Crystals in a Functionalized Unit's Perspective

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

---

Hydrogen bonding evolution and efficient blue light emission in a series of Zn-based organic–inorganic hybrid metal halide crystals

Science China Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

Language: Английский

---

Designing Polar Covalent Hybrid Cadmium‐Based Chalcohalides Ultraviolet Nonlinear Optical Crystal with Strong Optical Anisotropy via Double‐Site Dual FBUs Tailoring

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

Published: Jan. 26, 2025

The pressing demand for both established and innovative technologies to expand laser wavelengths has rendered high-performance nonlinear optical (NLO) crystals with large anisotropy indispensable. Here, centrosymmetric [SHC(NH2)2]2CdBr4 (1) pseudo-2D layered [SC(NH2)2]2CdBr2 (2), as well pseudo-3D noncentrosymmetric [SC(NH2)2]2CdCl2 (3) are successfully synthesized through the introduction of π-conjugated SC(NH2)2 groups. Compared ionic compound 1 containing full-halogen coordination tetrahedra, covalent compounds 2 3 featuring novel polar [SC(NH2)2]2CdX2 (X = Br, Cl) tetrahedral units demonstrate enhanced bandgaps (>4 eV) birefringences (>0.3@546 nm) due unique environment. Remarkably, exhibits a strong second-harmonic generation (SHG) response (2.1 × KH2PO4(KDP)), high laser-induced damage thresholds (30 AgGaS2(AGS), excellent water stability. birefringence is largest among hybrid halides NLO d10 metal cations. Detailed theoretical calculations confirm that such modified double-site dual functional building (FBUs) substitution an effective strategy designing superior materials SHG response, paving way development devices in related fields.

Language: Английский

---

From (C₆H₅N₂)₂CdCl₄ to (C₆H₅N₂)₂ZnCl₄, Chirality Transformation to Realize a Nonlinear Optical Organic–Inorganic Hybrid Halide with Balanced Comprehensive Performance

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

Published: Feb. 13, 2025

Nonlinear optical (NLO) crystals are critical for modern devices. In this study, two new hybrid metal halides, (C6H5N2)2CdCl4 (1) and (C6H5N2)2ZnCl4 (2), were synthesized by a mild solution method. 1 2 crystallize in different chiral space groups of P43212 P212121, respectively. Their crystal structures composed [MX4]2– (M = Cd, Zn) tetrahedrons (C6H5N2)+ cations with arrangements. They both have wide band gaps (3.98 3.83 eV). Attractively, exhibits SHG (second-harmonic generation) effect 1.2 × KDP, large birefringence (0.22@546 nm), high laser damage threshold (35 AgGaS2), can be grown up to centimeter level. Theoretical calculations show that these properties result from the ordered arrangement organic synergistic [MX4] tetrahedra, providing example develop high-performance NLO materials cation regulation.

Language: Английский

---

Chiral-Unit-Oriented Design of Non-π-Conjugated Noncentrosymmetric Phosphates with Short Absorption Edges

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 1881 - 1886

Published: Feb. 16, 2025

Deep ultraviolet (UV) nonlinear optical (NLO) crystals are important optoelectronic materials in high-tech applications. How to effectively design a noncentrosymmetric (NCS) structure, which is the rigorous prerequisite for second-order NLO crystals, remains great challenge. Introducing chiral methylpiperazine into phosphates achieved two polar phosphates, R- and S-(C5H14N2)(HPO4)·H2O. The units not only serve as structure-directing agents generating NCS structures but also do have negative impact on UV absorption, making maintain short absorption edges below 200 nm. They exhibit moderate activities of ∼0.5/0.6 KH2PO4 (KDP). Hirshfeld-surface analysis reveals that hydrogen-bonding along with Coulomb interactions rivet crystallization space group. Dipole moment calculations confirm direction macroscopic polarization. first-principles indicate properties mainly originate from synergistic interaction inorganic organic units. This study will provide useful insights targeted materials.

Language: Английский

---

Toward the Strongest Nonlinear Optical Response and Largest Birefringence in Solvent‐Free Organic–Inorganic Metal Halides by Hydrogen Bond Engineering

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

Published: March 5, 2025

Abstract Organic–inorganic metal halides (OIMHs) have emerged as a pivotal structural framework for discovering novel nonlinear optical (NLO) crystals, but the dominant role of inorganic components in NLO responses has become major bottleneck to performance improvement. In this study, protonation‐induced hydrogen‐bond engineering strategy is proposed introduce robust hydrogen‐bonding sites into organic group 4‐N,N‐dimethylamino‐4′‐N'‐methyl‐stilbazolium (DAMS + ) with strong effects. This approach promotes tight bonding and dense stacking between DAMS chain [Cd 2 Cl 6 ] n 2n− , leading synthesis growth new OIMHs‐type crystal [DAMS ‐Protonation]Cd ([DASH]Cd ). Enhanced hydrogen improves crystallinity prevents solvent infiltration, ensuring high stability below its melting point (232 °C). Additionally, protonation process induces twist dimethylamino DAMS⁺, which weakens π‐conjugation effect. alteration effectively broadens bandgap shifts UV cutoff edge 380 nm. Consequently, [DASH]Cd exhibits strongest second‐harmonic generation (SHG) response (19 × KH₂PO₄ @1064 nm) highest birefringence (0.36@550 among reported solvent‐free crystals. study demonstrates feasibility tuning properties through component OIMHs, offering insights regulation enhancement

Language: Английский

---

Zero-Dimensional Plastic Phase Transition Iron-Based Compounds with High T_c and Switchable SHG Responses

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

Published: March 14, 2025

Organic–inorganic hybrid materials have garnered significant interest due to their unique combination of phase transition characteristics, substantial entropy changes, simple preparation methods, and structural flexibility, making them promising candidates for applications in sensor technologies data storage systems. In the present research, two plastic organic–inorganic materials: [C7H17NF]FeCl4 (1) [C7H17NF]FeBr4 (2) were successfully synthesized by H/F substitution strategy. Significant step-like dielectric changes observed during reversible transitions 1 (401 K) 2 (406 K). At same time, flexible switchable SHG effects show characteristics band gap semiconductors with gaps 2.44 2.08 eV, respectively. This research presents an efficacious approach devising structures modulating properties materials.

Language: Английский

---

Tuning Covalent Bonding in Znic-Based Hybrid Halides towards Tunable Room-Temperature Phosphorescence

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

Published: Jan. 1, 2025

This work investigates organic–inorganic metal halides with room-temperature phosphorescence, showing that tuning the organic components and their interactions improves RTP performance for anti-counterfeiting applications.

Language: Английский

---

La₂Zn₃(SeO₃)₆: A UV Selenite Crystal with Second-Harmonic Generation and Large Birefringence

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

Published: May 1, 2025

Inorganic selenites are promising candidates for nonlinear optical and birefringent crystals. However, that can effectively transmit in the UV region still relatively scarce. In this study, we successfully synthesized first Zn-based selenite with properties using a hydrothermal method by introducing Zn2+ La3+ ions, which cause blue shift compound's bandgap, into system. The compound crystallizes chiral space group P3112 presents unique three-dimensional structure composed of two-dimensional zinc layers bridged LaO10 polyhedra. Notably, possesses wide bandgap (5.0 eV), high birefringence (0.092 at 546 nm), excellent thermal stability (∼540 °C), broad transparency window (0.21-6 μm), apparent SHG efficiency (0.2 × KDP). Our work not only demonstrates great potential as crystals but also expands research scope materials.

Language: Английский

---

Unveiling Noncentrosymmetric Pyridine Carboxylates from Centrosymmetric Templates through Motif Configuration Modulation in Zero-Dimensional System

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(47), P. 22620 - 22627

Published: Nov. 12, 2024

Developing approaches to induce noncentrosymmetric (NCS) frameworks through atomic-scale structural optimizations is crucial due the growing need for new ultraviolet (UV) nonlinear optical (NLO) materials. Herein, first two NCS pyridine carboxylates, ZnBr(C6H3.5FNO2)2 (1) and Cd(C6H3FNO2)2(H2O)2 (2), were successfully synthesized using centrosymmetric (CS) templates rational reconstructions induced by different ionic radius. Both compounds crystallize in orthorhombic system feature metal-centered zero-dimensional (0D) isolated clusters. Substituting [ZnO2N2O] pyramid CS carboxylate with [ZnO2N2Br] compound 1 breaks centrality, leading an framework a second harmonic generation (SHG) response of 1.7 × KH2PO4 (KDP). Introducing larger Cd2+ cation results trans-to-cis transition [MO4N2] (M = Zn, Co, Ni templates, Cd 2) octahedra, forming wing-shaped asymmetric 0D cluster SHG 2.1 KDP. These findings indicate approach that can effectively structures organic–inorganic hybrid

Language: Английский

---