Incorporating polyoxometalates and organic ligands to pursue 3d-4f heterometallic clusters: a series of {Cr4Ln4} clusters stabilized by phthalic acid and [SiW12O40]4

Ya-Nan Gu; Dan Zhao; Hao Yu; Rui Ge; Zhong Li; Chong-Bian Tian; Xin-Xiong Li; Yan-Qiong Sun; Shou-Tian Zheng

doi:10.1039/c9ra01731c

Incorporating polyoxometalates and organic ligands to pursue 3d-4f heterometallic clusters: a series of {Cr₄Ln₄} clusters stabilized by phthalic acid and [SiW₁₂O₄₀]⁴

RSC Adv. 2019 May 1;9(24):13543-13549. doi: 10.1039/c9ra01731c. eCollection 2019 Apr 30.

Authors

Ya-Nan Gu¹, Dan Zhao², Hao Yu¹, Rui Ge¹, Zhong Li¹, Chong-Bian Tian³, Xin-Xiong Li¹, Yan-Qiong Sun¹, Shou-Tian Zheng¹

Affiliations

¹ State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University Fuzhou Fujian 350108 China lxx@fzu.edu.cn stzheng@fzu.edu.cn.
² Fuqing Branch of Fujian Normal University Fuqing Fujian 350300 China.
³ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350108 China.

Abstract

By introduction of trilacunary Keggin-type polyoxometalate to the hydrothermal reaction system of Cr³⁺, Ln³⁺ and phthalic acid, a series of novel {Cr₄Ln₄} heterometallic clusters with the formula Cs₂[Cr₄Ln₄(μ₄-O)₄(μ₃-O)₄(C₈H₄O₄)₄(H₂O)₁₂](H₃SiW₁₂O₄₀)Cl·23H₂O (1-Ln, Ln = Ce, Pr, Nd) and [Cr₄Ln₄(μ₄-O)₄(μ₃-O)₄(C₈H₄O₄)₄(H₂O)₁₀](H₆SiW₁₂O₄₀)Cl₂·18H₂O (2-Ln, Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er) have been obtained. Single-crystal structural analyses show that 1-Ln and 2-Ln constitute the first cases of Cr-Ln heterometallic clusters stabilized by inorganic polyoxometalate anions and organic ligands. Optical spectra studies demonstrate that 1-Ln and 2-Ln are narrow-gap semiconductors with band gaps of about 1.5 eV. Magnetic investigation shows that compound 2-Dy is a potential single molecule magnet.