K<sub>5</sub>NaZr<sub>4</sub>F<sub>22</sub>(H<sub>2</sub>O)<sub>2</sub>: A Hydrated Zirconium Fluoride with a Second-Harmonic Generation Effect and a Short Ultraviolet Cutoff Edge Induced by Cosubstitution with Heterovalent Cations
The development of nonlinear optical (NLO) crystal materials with short ultraviolet cutoff edges is of great significance to laser applications and industrial development. Based on acentric AE-M-F<sub>22</sub> (Sr<sub>5</sub>Zr<sub>3</sub>F<sub>22</sub> (<b>1</b>), Ca<sub>5</sub>Zr<sub>3</sub>F<sub>22</sub> (<b>2</b>), and Ca<sub>5</sub>Hf<sub>3</sub>F<sub>22</sub> (<b>3</b>), with AE = alkaline earth metal and M = Zr, Hf), a novel hydrated zirconium-based fluoride, K<sub>5</sub>NaZr<sub>4</sub>F<sub>22</sub>(H<sub>2</sub>O)<sub>2</sub> (<b>4</b>), was obtained through a cosubstitution strategy involving mixed alkali metal cations. K<sub>5</sub>NaZr<sub>4</sub>F<sub>22</sub>(H<sub>2</sub>O)<sub>2</sub> crystallizes in the <i>C</i>2 space group and presents a unique three-dimensional {[Zr<sub>4</sub>F<sub>22</sub>(H<sub>2</sub>O)<sub>2</sub>]<sup>6-</sup>}<sub>∞</sub> anion framework composed of hydrogen-bonded {[Zr<sub>4</sub>F<sub>23</sub>(H<sub>2</sub>O)<sub>2</sub>]<sup>7-</sup>}<sub>∞</sub> chains. <b>1</b>-<b>4</b> exhibit phase-matched second-harmonic generation (SHG) responses and short ultraviolet cutoff edges. This work has brought about a novel structure of zirconium fluoride and enriched the family of NLO zirconium/hafnium fluorides.
Authors
- Ru‐Ling Tang (ORCID: https://orcid.org/0000-0001-5707-8288)
- Wenfeng Zhou
- Ling Wang (ORCID: https://orcid.org/0000-0002-7621-2312)
- Wenlong Liu (ORCID: https://orcid.org/0000-0002-8514-6812)
- Bing-Wei Miao
- Guo-Ren Zhu
Institutions
- Yangzhou University (CN)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-08-27
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c03483
- Citations
- 2
- Primary Topic
- Crystal Structures and Properties
- Type
- article
- Field-Weighted Citation Impact
- 0.85