We report four new copper-rich open-framework chalcogenides(COCs)with the formulas[Cu_(8)Ge_(6)Se_(19)](C_(5)H_(12)N)_(6)(1a),[Cu_(8)Sn_(6)Se_(19)](C_(6)H_(12)N_(2))_(4)(H_(2)O)_(13)(1b),[Cu_(16)Ge_(12)S_(36)][Ni(en)_...We report four new copper-rich open-framework chalcogenides(COCs)with the formulas[Cu_(8)Ge_(6)Se_(19)](C_(5)H_(12)N)_(6)(1a),[Cu_(8)Sn_(6)Se_(19)](C_(6)H_(12)N_(2))_(4)(H_(2)O)_(13)(1b),[Cu_(16)Ge_(12)S_(36)][Ni(en)_(3)]_(4)(en)xCl1.5(1c),and[Cu_(7)Ge_(4)Se_(13)](C_(6)H_(21)N_(4))(2).Single-crystal X-ray diffraction analyses suggest that all of these compounds with pcu-type topology are completely built on icosahedral clusters.Of particular interest,the connection units linking the icosahedral clusters in 1a-1c are pure dimeric units in three axial directions.Such a case is unprecedented among previously reported COCs and pushes up the length limit of the connection mode,thereby resulting in the largest solvent-accessible space in COCs.Compound 2 is built on an intriguing and unprecedented mixed-metal Cu_(7)GeSe_(13) cluster.The copper-rich nature of these compounds gives rise to a narrow band gap in the near-infrared range,making them hold promise for photoelectric applications.展开更多
基金National Natural Science Foundation of China(No.21271135,21671142)a start-up fund(Q410900712)from Soochow University+3 种基金Jiangsu Province Natural Science Fund for Distinguished Young Scholars(BK20160006)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)Young Thousand Talented ProgramH.-J.Y.was supported by Jiangsu Planned Projects for Postdoctoral Research Fund No.1501095B.
文摘We report four new copper-rich open-framework chalcogenides(COCs)with the formulas[Cu_(8)Ge_(6)Se_(19)](C_(5)H_(12)N)_(6)(1a),[Cu_(8)Sn_(6)Se_(19)](C_(6)H_(12)N_(2))_(4)(H_(2)O)_(13)(1b),[Cu_(16)Ge_(12)S_(36)][Ni(en)_(3)]_(4)(en)xCl1.5(1c),and[Cu_(7)Ge_(4)Se_(13)](C_(6)H_(21)N_(4))(2).Single-crystal X-ray diffraction analyses suggest that all of these compounds with pcu-type topology are completely built on icosahedral clusters.Of particular interest,the connection units linking the icosahedral clusters in 1a-1c are pure dimeric units in three axial directions.Such a case is unprecedented among previously reported COCs and pushes up the length limit of the connection mode,thereby resulting in the largest solvent-accessible space in COCs.Compound 2 is built on an intriguing and unprecedented mixed-metal Cu_(7)GeSe_(13) cluster.The copper-rich nature of these compounds gives rise to a narrow band gap in the near-infrared range,making them hold promise for photoelectric applications.
