Chiral Metal Self‐assemblies of Zirconium‐Tetrahedra and Their Second Harmonic Generation Activity DOI
Ermeng Han,

Y.J. Li,

Tun Wu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract The chirality of metal‐organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units the construction noncentrosymmetric materials. Herein, by self‐assembling 4,4′,4′′‐nitrilotribenzoic acid (H 3 NBA) with bis(cyclopentadienyl)‐zirconium dichloride (Cp 2 ZrCl , Cp=η 5 ‐C H ) different solvent conditions, we have obtained three hierarchical packing modes metallo‐tetrahedra distinct spatial symmetry groups (designated as Zr‐α, Zr‐β, and Zr‐γ). Among them, Zr‐α employs a simple cubic arrangement common centrosymmetric superstructure, which consists pair equimolar enantiomers its unit cell. While Zr‐β results conglomerates spontaneous resolution without using any resolving agents, giving rise two enantiopure entities separately (Zr‐β‐ P Zr‐β‐ M ). More importantly, Zr‐γ breaks inversion center crystallizes into racemic yet non‐centrosymmetric superstructure face‐centered mode. Based on nature, displayed good second harmonic generation activities. This work presents successful instance wherein reaction induces modulation intermolecular mode afford solid materials, can greatly promote development (NCS)

Language: Английский

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
Recent progress in structural design strategies of high-birefringence optical crystals DOI
Alan Xu,

Mao‐Yin Ran,

Xintao Wu

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 540, P. 216775 - 216775

Published: May 8, 2025

Language: Английский

Citations

0
La3(Ga3S3O3)(Si2O7): An Oxychalcogenide Demonstrating Ultrawide Optical Bandgap and Favorable Birefringence Propelled by Divergent Anionic Groups DOI

Ming‐Shu Zhang,

Shao‐Min Pei,

Xiao‐Ming Jiang

et al.

ACS Materials Letters, Journal Year: 2024, Volume and Issue: 7(1), P. 312 - 318

Published: Dec. 19, 2024

The exceptional structural plasticity and well-balanced properties of oxychalcogenides make them highly desirable as infrared nonlinear optical (IR NLO) materials. A breakthrough in the design high-performance involves integrating assembling multiple anionic units to maximize their functions. Following this approach, we developed La3(Ga3S3O3)(Si2O7) (LGSSO) by simultaneously incorporating [Ga3O3S6] [Si2O7] groups. potential LGSSO an IR NLO material is evident from its wide bandgap (4.82 eV, runner-up oxychalcogenides), high laser-induced damage threshold (8.7 × AgGaS2 at 1064 nm), attractive birefringence (0.122 546 moderate phase-matching second-harmonic generation response (1.7 KH2PO4 nm, 0.3 1910 nm). Theoretical studies indicate that [LaS2O6] [GaO2S2] contribute significantly coefficient, while trimers with pronounced polarizability anisotropy play a pivotal role providing substantial birefringence. This work offers tangible paradigm for exploring well-performed oxychalcogenide material.

Language: Английский

Citations

1
Chiral Metal Self‐assemblies of Zirconium‐Tetrahedra and Their Second Harmonic Generation Activity DOI
Ermeng Han,

Y.J. Li,

Tun Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract The chirality of metal‐organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units the construction noncentrosymmetric materials. Herein, by self‐assembling 4,4′,4′′‐nitrilotribenzoic acid (H 3 NBA) with bis(cyclopentadienyl)‐zirconium dichloride (Cp 2 ZrCl , Cp=η 5 ‐C H ) different solvent conditions, we have obtained three hierarchical packing modes metallo‐tetrahedra distinct spatial symmetry groups (designated as Zr‐α, Zr‐β, and Zr‐γ). Among them, Zr‐α employs a simple cubic arrangement common centrosymmetric superstructure, which consists pair equimolar enantiomers its unit cell. While Zr‐β results conglomerates spontaneous resolution without using any resolving agents, giving rise two enantiopure entities separately (Zr‐β‐ P Zr‐β‐ M ). More importantly, Zr‐γ breaks inversion center crystallizes into racemic yet non‐centrosymmetric superstructure face‐centered mode. Based on nature, displayed good second harmonic generation activities. This work presents successful instance wherein reaction induces modulation intermolecular mode afford solid materials, can greatly promote development (NCS)

Language: Английский

Citations

0
Chiral Metal Self‐assemblies of Zirconium‐Tetrahedra and Their Second Harmonic Generation Activity DOI
Ermeng Han,

Y.J. Li,

Tun Wu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract The chirality of metal‐organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units the construction noncentrosymmetric materials. Herein, by self‐assembling 4,4′,4′′‐nitrilotribenzoic acid (H 3 NBA) with bis(cyclopentadienyl)‐zirconium dichloride (Cp 2 ZrCl , Cp=η 5 ‐C H ) different solvent conditions, we have obtained three hierarchical packing modes metallo‐tetrahedra distinct spatial symmetry groups (designated as Zr‐α, Zr‐β, and Zr‐γ). Among them, Zr‐α employs a simple cubic arrangement common centrosymmetric superstructure, which consists pair equimolar enantiomers its unit cell. While Zr‐β results conglomerates spontaneous resolution without using any resolving agents, giving rise two enantiopure entities separately (Zr‐β‐ P Zr‐β‐ M ). More importantly, Zr‐γ breaks inversion center crystallizes into racemic yet non‐centrosymmetric superstructure face‐centered mode. Based on nature, displayed good second harmonic generation activities. This work presents successful instance wherein reaction induces modulation intermolecular mode afford solid materials, can greatly promote development (NCS)

Language: Английский

Citations

0