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Keywords:

  • Chalcogenides;
  • Copper-rich framework;
  • Selenoarsenates;
  • Icosahedral clusters

Abstract

Three copper-rich framework selenoarsenates, (H2en)1.5[Cu88-Se)(AsSe4)6/2] (1), (H2dap)1.5[Cu88-Se)(AsSe4)6/2] (2), and Na2(H2dap)0.5[Cu88-Se)(AsSe4)6/2] (3), were synthesized under solvothermal conditions. These three compounds are isostructural and contain a 3D Cu-As-Se framework constructed from novel icosahedral Cu8Se13 clusters linked by As5+, with counterions located in the cavities. The icosahedral Cu8Se13 clusters represent the first icosahedral Cu-Se unit found in 3D framework chalcogenides, and contain an unusual μ8-cubic bridging Se2– ion at the core site. The covalent 3D Cu-As-Se framework is rigid and not sensitive to the shape and charge density of counterions.