Quantum mechanics

High harmonic generation

Crystal (programming language)

Materials science

Chromatography

Infrared

Single crystal

Mid infrared

Computer science

Wavelength

Band gap

Laser

Physics

Nonlinear system

Organic chemistry

Optics

Nonlinear optical

Nonlinear optics

Analytical Chemistry (journal)

Crystallography

Chemistry

Programming language

Second-harmonic generation

Infrared spectroscopy

Optoelectronics

Angewandte Chemie International Edition

To design high‐performance mid‐infrared (mid‐IR) nonlinear optical (NLO) materials, we have focused on the combination of a heavy metal lone pair cation, Pb 2+ and mixed oxyhalides. A systematic investigation in PbO‐PbCl 2 ‐PbBr 2 system led us to discover the first examples of NLO lead mixed oxyhalides, namely, Pb 13 O 6 Cl 4 Br 10 , Pb 13 O 6 Cl 7 Br 7 , and Pb 13 O 6 Cl 9 Br 5 . All the reported materials have remarkably comprehensive properties including broad IR transparency (up to 14.0 μm), qualified second harmonic generation (SHG) responses (0.6–0.9×AgGaS 2 ), wide band gaps (3.05–3.21 eV), and ease of crystal growth. Interestingly, a centimeter‐sized single crystal (2.9×1.3×0.5 cm 3 ) of Pb 13 O 6 Cl 9 Br 5 revealing a wide transparent range (0.384–14.0 μm) and high laser damage threshold (LDT) (14.6×AgGaS 2 ) has been successfully grown in an open system. The study suggests that all the reported mixed oxyhalides are outstanding candidates for mid‐IR NLO materials.

Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials