Na2BaB12O18F4: A Mixed Alkali/Alkaline-Earth Metal Fluorooxoborate with Two Unprecedented Interpenetrating Three-Dimensional B-O/F Anionic Networks and a Short Ultraviolet Cutoff Edge

Tuohetijiang Baiheti; Abudukadi Tudi; Minqiang Gai; Xuping Wang; Shujuan Han

doi:10.1021/acs.inorgchem.3c00203

Na₂BaB₁₂O₁₈F₄: A Mixed Alkali/Alkaline-Earth Metal Fluorooxoborate with Two Unprecedented Interpenetrating Three-Dimensional B-O/F Anionic Networks and a Short Ultraviolet Cutoff Edge

Inorg Chem. 2023 Mar 27;62(12):5008-5015. doi: 10.1021/acs.inorgchem.3c00203. Epub 2023 Mar 16.

Authors

Tuohetijiang Baiheti^{1

2}, Abudukadi Tudi^{1

2}, Minqiang Gai^{1

2}, Xuping Wang^{1

2}, Shujuan Han^{1

2}

Affiliations

¹ Research Center for Crystal Materials, CAS Key Laboratory of Functional Materials and Devices for Special Environments, Xinjiang Key Laboratory of Electronic Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry of CAS, Urumqi 830011, China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.

PMID: 36926852
DOI: 10.1021/acs.inorgchem.3c00203

Abstract

Fluorooxoborates are promising yet largely untapped crystal materials for linear and nonlinear optical applications. The introduction of a strong electronegative F atom into an oxyboron anionic group offers a virtually unlimited chance for structural engineering and ultimately purposeful tuning of the macroscopic optical properties of the crystal. Herein, a new mixed alkali/alkaline-earth fluorooxoborate, Na₂BaB₁₂O₁₈F₄, was synthesized in a closed system. Na₂BaB₁₂O₁₈F₄ features a [B₆O₁₁F₂] fundamental building unit (FBB), which polymerizes into two new (first example) independent interpenetrating three-dimensional (3D) B-O/F anionic networks constructed entirely from BO₃ and BO₃F units. Based on optical characterizations and the first-principles calculations, Na₂BaB₁₂O₁₈F₄ exhibits a moderate birefringence (0.054 @ 1064 nm) and a short ultraviolet (UV) cutoff edge (below 190 nm). The successful synthesis and characterization of Na₂BaB₁₂O₁₈F₄ may speed up the subsequent discovery of other mixed alkali/alkaline-earth metal fluorooxoborates.