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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Published on: March 24, 2018

KF·[SO₂(NH₂)₂]: the First Deep-Ultraviolet Transparent Sulfonamide Fluoride Nonlinear Optical Crystal with Novel

Yuchen Yan¹, Xin Wen², Piao Tang¹

¹State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China.

Angewandte Chemie (International Ed. in English)

|September 15, 2025

Summary

Researchers developed a new method to create advanced nonlinear optical (NLO) crystals using sulfonamide fluoride. This new material shows strong second-harmonic generation and birefringence for deep-ultraviolet applications.

Keywords:

Cairo pentagonal structure Deep ultraviolet Nonlinear optical crystal Second harmonic generation Sulfonamide fluoride

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Area of Science:

Materials Science
Solid-State Chemistry
Optics

Background:

The sulfonamide group (SO₂(NH₂)₂) possesses high hyperpolarizability and anisotropy, making it promising for deep-ultraviolet nonlinear optical (NLO) crystals.
However, its neutral nature and limited protonation hinder its practical application in NLO materials.

Purpose of the Study:

To introduce an ionic framework using halide salts to stabilize sulfonamide molecules and control their orientation.
To enable desirable second-harmonic generation (SHG) and birefringence properties in novel NLO crystals.

Main Methods:

Synthesis of the first sulfonamide fluoride, KF·[SO₂(NH₂)₂], by incorporating sulfonamide units into a KF lattice.
Characterization of the crystal structure, including K─O ionic and N─H···F hydrogen bonds, and analysis of its NLO properties.

Main Results:

Successful synthesis of KF·[SO₂(NH₂)₂] with a unique Cairo pentagonal configuration.
Observed strong second-harmonic generation (SHG) response (1.4 × KDP) at 1064 nm.
Achieved large birefringence (0.079 at 546 nm) and a short cutoff edge (<190 nm).

Conclusions:

The proposed design strategy effectively stabilizes sulfonamide molecules and enhances NLO properties.
KF·[SO₂(NH₂)₂] represents a promising new material for deep-ultraviolet NLO applications.
This work paves the way for designing advanced NLO crystals incorporating the sulfonamide group.