Design, Synthesis, and Improvement of Nonlinear Optical Properties from Aluminophosphite to Aluminophosphate
Two novel aluminophosphates, Al<sub>2</sub>(HPO<sub>3</sub>)<sub>2.26</sub>(HPO<sub>4</sub>)<sub>0.74</sub> and Al<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>, were synthesized using hydrothermal methods, while another polar aluminophosphite, Al[P<sub>2</sub>O<sub>3</sub>(OH)<sub>3</sub>](H<sub>2</sub>O), was obtained via a low-temperature flux method. They crystallized in the nonpolar space group <i>P</i>6<sub>3</sub><i>/m</i> and polar space groups of <i>P</i>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub> and <i>P</i>6<sub>3</sub>mc, respectively. The basic units of Al<sub>2</sub>(HPO<sub>3</sub>)<sub>2.26</sub>(HPO<sub>4</sub>)<sub>0.74</sub> consist of PO<sub>4</sub>/PO<sub>3</sub> and AlO<sub>6</sub> groups, in which one AlO<sub>6</sub> octahedron coordinated with six PO<sub>4</sub> tetrahedra/PO<sub>3</sub> pyramids and one PO<sub>4</sub> tetrahedron/PO<sub>3</sub> pyramid linked three Al<sub>2</sub>O<sub>9</sub> dimers. However, the fundamental units for Al<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub> are PO<sub>4</sub> tetrahedra, AlO<sub>6</sub> octahedra, and AlO<sub>5</sub> trigonal bipyramids, in which one PO<sub>4</sub> tetrahedron is connected with three Al<sub>2</sub>O<sub>10</sub> dimers and one Al<sub>2</sub>O<sub>10</sub> dimer is linked with six PO<sub>4</sub> tetrahedra, forming its novel three-dimensional framework structure. Importantly, Al[P<sub>2</sub>O<sub>3</sub>(OH)<sub>3</sub>](H<sub>2</sub>O) and Al<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub> demonstrate moderate second-harmonic generation effects in the UV region, with ∼0.15 and ∼0.68 × KDP, respectively. The syntheses and topological structures, compositional analysis, thermal behavior, FT-IR spectral characterization, Raman spectral analysis, and UV-vis diffuse reflectance along with the NLO performances of Al<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub> and Al[P<sub>2</sub>O<sub>3</sub>(OH)<sub>3</sub>](H<sub>2</sub>O) are discussed.
Authors
- Hongdian Lu (ORCID: https://orcid.org/0000-0002-8630-9740)
- Cheng Hou (ORCID: https://orcid.org/0000-0003-2967-0326)
- Wei Cheng (ORCID: https://orcid.org/0000-0002-5297-7046)
- Yucheng Hao (ORCID: https://orcid.org/0000-0001-5281-1751)
- Mingli Liang (ORCID: https://orcid.org/0000-0002-1854-7026)
- Changlin Chen (ORCID: https://orcid.org/0009-0009-8808-0861)
- Xi Zhao
- Yuan Lin (ORCID: https://orcid.org/0000-0002-6243-6948)
- Kunhong Hu (ORCID: https://orcid.org/0000-0003-0478-9064)
- Rongfang Zhang
Institutions
- Fujian Normal University (CN)
- Hefei University (CN)
- Nanjing University of Posts and Telecommunications (CN)
- Beike Biotechnology (China) (CN)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-06-27
- DOI
- https://doi.org/10.1021/acs.inorgchem.5c01496
- Citations
- 1
- Primary Topic
- Crystal Structures and Properties
- Type
- article
- Field-Weighted Citation Impact
- 0.43
Funders
- National Natural Science Foundation of China
- Natural Science Foundation of Fujian Province
- Hefei University
- Anhui Provincial Department of Education
- State Key Laboratory of Structural Chemistry
- Natural Science Research of Jiangsu Higher Education Institutions of China