Novel three-dimensional(3D)inorganic chalcogenide architectures have attracted much attention because of their rich structural assembly patterns and intriguing physical properties.Herein,four isostructural quaternary ...Novel three-dimensional(3D)inorganic chalcogenide architectures have attracted much attention because of their rich structural assembly patterns and intriguing physical properties.Herein,four isostructural quaternary semiconducting chalcogenides,namely Cs_(4)[RE_(26)Cd_(7)Se_(48)](RE=Ho,Er,Tm,and Lu),have been discovered and found to crystallize in a tetragonal system,space group I41/a(no.88).Their structures feature 3D quasi-NaCl type architectures formed by edge-sharing and face-sharing of[RESe_(6)]and[MSe_(6)](M=RE/Cd)octahedra,which are embedded with the unprecedented polyanionic[Cs_(2)@Se_(18)–Cd–Cs_(2)@Se_(18)]closed cavities.Significantly,the compound Cs4[Ho_(26)Cd_(7)Se_(48)]exhibits ultralow thermal conductivity(0.38–0.29 W m^(−1)K^(−1))from 295 K to 675 K,which is one of the lowest values reported in crystalline chalcogenides.This result not only enriches the coordination chemistry of host–vip systems,but also suggests a new thought for the design of novel inorganic chalcogenides with intrinsic low thermal conductivities.展开更多
基金supported by the National Natural Science Foundation of China(22005304,21771179 and 21901246)the Natural Science Foundation of Fujian Province(No.2019J01133)the Program of State Key Laboratory of Quantum Optics and Quantum Optics Devices(No.KF201904).
文摘Novel three-dimensional(3D)inorganic chalcogenide architectures have attracted much attention because of their rich structural assembly patterns and intriguing physical properties.Herein,four isostructural quaternary semiconducting chalcogenides,namely Cs_(4)[RE_(26)Cd_(7)Se_(48)](RE=Ho,Er,Tm,and Lu),have been discovered and found to crystallize in a tetragonal system,space group I41/a(no.88).Their structures feature 3D quasi-NaCl type architectures formed by edge-sharing and face-sharing of[RESe_(6)]and[MSe_(6)](M=RE/Cd)octahedra,which are embedded with the unprecedented polyanionic[Cs_(2)@Se_(18)–Cd–Cs_(2)@Se_(18)]closed cavities.Significantly,the compound Cs4[Ho_(26)Cd_(7)Se_(48)]exhibits ultralow thermal conductivity(0.38–0.29 W m^(−1)K^(−1))from 295 K to 675 K,which is one of the lowest values reported in crystalline chalcogenides.This result not only enriches the coordination chemistry of host–vip systems,but also suggests a new thought for the design of novel inorganic chalcogenides with intrinsic low thermal conductivities.
