Two new cadmium sulfamates,namely,centrosymmetric Cd(NH_(2)SO_(3))_(2)·2H_(2)O and noncentrosymmetric Cd(NH_(2)SO_(3))_(2) have been successfully synthesized.Crystals of Cd(NH_(2)SO_(3))_(2)·2H_(2)O grown us...Two new cadmium sulfamates,namely,centrosymmetric Cd(NH_(2)SO_(3))_(2)·2H_(2)O and noncentrosymmetric Cd(NH_(2)SO_(3))_(2) have been successfully synthesized.Crystals of Cd(NH_(2)SO_(3))_(2)·2H_(2)O grown using an aquasolution method reveal an infinite chain structure consisting of trans-[CdO_(2)(H_(2)O)_(2)(NH_(2))_(2)]octahedra and[NH_(2)SO_(3)]units.Crystals of Cd(NH_(2)SO_(3))_(2) obtained during the process of dehydration of Cd(NH_(2)SO_(3))_(2)·2H_(2)O exhibit a 3D framework composed of cis-[CdO_(4)(NH_(2))_(2)]octahedra and[NH_(2)SO_(3)]tetrahedra.Temperature-and humidity-induced reversible phase transitions of the title compounds are observed,which is confirmed by TGA and PXRD.Cd(NH_(2)SO_(3))_(2) exhibits a phase-matchable SHG response of ca.0.15×KDP.Interestingly,nitrogen-containing[CdO_(4)N_(2)]octahedra are found in the metal sulfamates for the first time.The unique arrangement is discussed with the hard-and-soft acids and bases theory and further compared with other existing[MO_(6)](M=Na,Mg)octahedra in sulfamates.In addition,the discovery would provide a new perspective to design new materials by adjusting the structural arrangement for polar anionic groups.展开更多
基金supported by the National Research Foundation of Korea(NRF)funded by the Ministry of ScienceICT(Grant No.2018R1A5A1025208 and 2019R1A2C3005530).
文摘Two new cadmium sulfamates,namely,centrosymmetric Cd(NH_(2)SO_(3))_(2)·2H_(2)O and noncentrosymmetric Cd(NH_(2)SO_(3))_(2) have been successfully synthesized.Crystals of Cd(NH_(2)SO_(3))_(2)·2H_(2)O grown using an aquasolution method reveal an infinite chain structure consisting of trans-[CdO_(2)(H_(2)O)_(2)(NH_(2))_(2)]octahedra and[NH_(2)SO_(3)]units.Crystals of Cd(NH_(2)SO_(3))_(2) obtained during the process of dehydration of Cd(NH_(2)SO_(3))_(2)·2H_(2)O exhibit a 3D framework composed of cis-[CdO_(4)(NH_(2))_(2)]octahedra and[NH_(2)SO_(3)]tetrahedra.Temperature-and humidity-induced reversible phase transitions of the title compounds are observed,which is confirmed by TGA and PXRD.Cd(NH_(2)SO_(3))_(2) exhibits a phase-matchable SHG response of ca.0.15×KDP.Interestingly,nitrogen-containing[CdO_(4)N_(2)]octahedra are found in the metal sulfamates for the first time.The unique arrangement is discussed with the hard-and-soft acids and bases theory and further compared with other existing[MO_(6)](M=Na,Mg)octahedra in sulfamates.In addition,the discovery would provide a new perspective to design new materials by adjusting the structural arrangement for polar anionic groups.
