Solvothermal synthesis, structure and physical properties of Cs[Cr(en)2MSe4] (M = Ge, Sn) with [MSe4]4− tetrahedra as chelating ligand

Yingqi Wang; Ruiqi Wang; Qinglong Liu; Xiaofang Lai; Xian Zhang; Haijie Chen; Chong Zheng; Jianhua Lin; Fuqiang Huang

doi:10.1039/C6DT00233A

Solvothermal synthesis, structure and physical properties of Cs[Cr(en)₂MSe₄] (M = Ge, Sn) with [MSe₄]⁴⁻ tetrahedra as chelating ligand†

Yingqi Wang,^a Ruiqi Wang,^b Qinglong Liu,^b Xiaofang Lai,^b Xian Zhang,^b Haijie Chen,^c Chong Zheng,*^d Jianhua Lin^b and Fuqiang Huang*^bc

Author affiliations

* Corresponding authors

^a Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, P. R. China

^b Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
E-mail: huangfq@pku.edu.cn

^c Department CAS Key Laboratory of Materials for Energy Conversion Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, P.R. China

^d Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, USA
E-mail: czheng@niu.edu

Abstract

Two chromium chalcogenide Cs[Cr(en)₂GeSe₄] (1) and Cs[Cr(en)₂SnSe₄] (2) have been synthesized by a solvothermal method. Both compounds crystallize in the monoclinic space group P2₁/n. The structures of the two compounds are characterized by isolated [Cr(en)₂MSe₄]⁻ clusters separated by Cs⁺ ions. The optical properties of the two compounds were measured which indicate a similar band gap of 1.58 eV. DFT calculations demonstrated that the valance band maximum (VBM) consist of Cr 3d orbitals and Se 4p orbitals while the conductive band minimum (CBM) are composed of Cr 3d orbitals for both compounds, which explains their similar optical band gap energies. Both compounds possess paramagnetic behaviors with the effective magnetic moment of 3.97μ_B for Cs[Cr(en)₂GeSe₄] and 3.91μ_B for Cs[Cr(en)₂SnSe₄], respectively. Field-dependent magnetization measurements demonstrated their potential as magnetocaloric materials, with the magnetic entropy change of 11.6 J (kg K)⁻¹ for Cs[Cr(en)₂GeSe₄], and 14.2 J (kg K)⁻¹ for Cs[Cr(en)₂SnSe₄].

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Article information

https://doi.org/10.1039/C6DT00233A

Submitted

18 Jan 2016

Accepted

19 Apr 2016

First published

19 Apr 2016

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Dalton Trans., 2016,45, 9097-9102

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Paper

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Solvothermal synthesis, structure and physical properties of Cs[Cr(en)₂MSe₄] (M = Ge, Sn) with [MSe₄]⁴⁻ tetrahedra as chelating ligand

Y. Wang, R. Wang, Q. Liu, X. Lai, X. Zhang, H. Chen, C. Zheng, J. Lin and F. Huang, Dalton Trans., 2016, 45, 9097

DOI: 10.1039/C6DT00233A

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