NaREP2Se6 (RE = Y, Sm, Gd-Dy): Quaternary Rare-Earth Selenophosphates with Unique 3D {[REP2Se6]-}∞ Framework Built by RESe8 and P2Se6 Motifs and Multiple Properties

Chen-Yi Zhao; Zi-Xia Chen; Wen-Dong Yao; Wenfeng Zhou; Wenlong Liu; Sheng-Ping Guo

doi:10.1021/acs.inorgchem.3c03695

NaREP₂Se₆ (RE = Y, Sm, Gd-Dy): Quaternary Rare-Earth Selenophosphates with Unique 3D {[REP₂Se₆]^-}_∞ Framework Built by RESe₈ and P₂Se₆ Motifs and Multiple Properties

Inorg Chem. 2023 Dec 11;62(49):19843-19847. doi: 10.1021/acs.inorgchem.3c03695. Epub 2023 Nov 30.

Authors

Chen-Yi Zhao¹, Zi-Xia Chen¹, Wen-Dong Yao¹, Wenfeng Zhou¹, Wenlong Liu¹, Sheng-Ping Guo¹

Affiliation

¹ School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, People's Republic of China.

PMID: 38032849
DOI: 10.1021/acs.inorgchem.3c03695

Abstract

Rare-earth (RE) chalcophosphates have been widely studied because of their abundant structures. Here, five new RE selenophosphates, NaREP₂Se₆ (RE = Y, Sm, Gd-Dy), were synthesized by a facile RE oxide-boron-selenium solid-state route. They crystallize in the triclinic P1̅ space group, featuring three-dimensional (3D) structures constructed by RESe₈ and P₂Se₆ motifs, different from common 2D RE chalcophosphates A-RE-P₂-Q₆ (A = alkali metal; Q = S, Se) system. Their structural chemistry and relationship with related phases are analyzed. Both the size of A and the coordination geometry of RE have important influences on the system's structures. Their optical band gaps are tunable from 1.79 to 2.50 eV, and they exhibit diverse magnetic behaviors, including Van-Vleck-type paramagnetism, antiferromagnetism, and ferromagnetism. Their photocurrent responses and thermal stabilities are analyzed as well. Calculation results suggest that the RESe₈ and P₂Se₆ units make a great contribution to the optical properties. This work enriches the chemistry and multifunctional properties of RE chalcophosphates.