KF·[SO <sub>2</sub> (NH <sub>2</sub> ) <sub>2</sub> ]: the First Deep‐Ultraviolet Transparent Sulfonamide Fluoride Nonlinear Optical Crystal with Novel Cairo Pentagonal Structure

Y Yuchen Yan X Xin Wen P Piao Tang (State 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) J Jingyao Lu (State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal Tianjin University of Technology Tianjin 300384 China) J Jindong Chen (State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Materials Science and Engineering) J Jiyang Wang (State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals) Z Zhanggui Hu (State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals) N Ning Ye (State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Materials Science and Engineering) G Guang Peng (State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Materials Science and Engineering)

Abstract

Abstract The sulfonamide group (SO 2 (NH 2 ) 2 ) shows great potential for deep‐ultraviolet nonlinear optical (NLO) crystals due to its strong hyperpolarizability and anisotropy, but its neutrality and poor protonation limit its application. Here, we propose a new design strategy that introduces an ionic framework via halide salts to both stabilize sulfonamide molecules and control their orientation, thereby enabling desirable second‐harmonic generation (SHG) and birefringence. Following this concept, the first sulfonamide fluoride, KF·[SO 2 (NH 2 ) 2 ], was successfully synthesized, with SO 2 (NH 2 ) 2 units firmly anchored in the KF lattice by K─O ionic and N─H···F hydrogen bonds. Remarkably, this crystal exhibits a unique and compact Cairo pentagonal configuration. Benefiting from its well‐ordered structure, the crystal exhibits a strong SHG response of 1.4 × KDP at 1064 nm, a large birefringence of 0.079@546 nm, and a short cutoff edge below 190 nm. This work opens new avenues for the design of advanced NLO crystals with a sulfonamide group.

Article Details

Volume / Issue Vol. 64, Issue 44
Published October 27, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (9)

Y

Yuchen Yan

X

Xin Wen

P

Piao Tang

State 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

J

Jingyao Lu

State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal Tianjin University of Technology Tianjin 300384 China

J

Jindong Chen

State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Materials Science and Engineering

J

Jiyang Wang

State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals

Z

Zhanggui Hu

State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystals

N

Ning Ye

State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Materials Science and Engineering

G

Guang Peng

State Key Laboratory of Crystal Materials, Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, College of Materials Science and Engineering