Thioantimonates containing high oxidation state Sb^(5+)have been proven to exhibit excellent performance in the design of new materials such as infrared optical crystals and lithium-ion batteries.However,as described ...Thioantimonates containing high oxidation state Sb^(5+)have been proven to exhibit excellent performance in the design of new materials such as infrared optical crystals and lithium-ion batteries.However,as described by the“inert pair effect”,the preparation of P-block elements containing high oxidation states in sealed systems has been a challenge.In this study,an aliovalent cation substitution strategy was used to design and synthesize three novel thioantimonates(V),A_(4)BaSb_(2)Se_(8)(A=Cs,Rb)and Rb_(2)BaSbS_(4)Cl(RBSSC),respectively,all of which contain rare[SbS_(4)]tetrahedral units.The introduction of Ba^(2+)ions leads to the distortion and high-density arrangement of[SbSe_(4)]units,which is manifested as a significant 3.7 times enhancement of the birefringence compared to that of the parent compound Cs_(3)SbSe_(4)(0.041→Cs_(4)BaSb_(2)Se_(8)0.150@1064 nm).By further introducing highly electronegative halogen atoms,the first antimony-based thiohalide(V)RBSSC was synthesized.Theoretical calculations show that the band gap of RBSSC is up to 3.674 eV,larger than those of all known antimony-based thiohalides(III).This work provides strong evidence that the aliovalent cation substitution strategy is an effective way to find new thioantimonate(V)families,and also indicates that the cation size effect introduced by elemental substitution may lead to surprising performance improvements.展开更多
基金supported by the Natural Science Foundation of the Xinjiang Uygur Autonomous Region(2022D01B206 and 2023D01A04)Shanghai Cooperation Organization Science and Technology Partnership Program(2023E01001)+1 种基金the National Natural Science Foundation of China(62305382 and 52302011)support from Tianchi Doctor Plan of Xinjiang Uygur Autonomous Region。
文摘Thioantimonates containing high oxidation state Sb^(5+)have been proven to exhibit excellent performance in the design of new materials such as infrared optical crystals and lithium-ion batteries.However,as described by the“inert pair effect”,the preparation of P-block elements containing high oxidation states in sealed systems has been a challenge.In this study,an aliovalent cation substitution strategy was used to design and synthesize three novel thioantimonates(V),A_(4)BaSb_(2)Se_(8)(A=Cs,Rb)and Rb_(2)BaSbS_(4)Cl(RBSSC),respectively,all of which contain rare[SbS_(4)]tetrahedral units.The introduction of Ba^(2+)ions leads to the distortion and high-density arrangement of[SbSe_(4)]units,which is manifested as a significant 3.7 times enhancement of the birefringence compared to that of the parent compound Cs_(3)SbSe_(4)(0.041→Cs_(4)BaSb_(2)Se_(8)0.150@1064 nm).By further introducing highly electronegative halogen atoms,the first antimony-based thiohalide(V)RBSSC was synthesized.Theoretical calculations show that the band gap of RBSSC is up to 3.674 eV,larger than those of all known antimony-based thiohalides(III).This work provides strong evidence that the aliovalent cation substitution strategy is an effective way to find new thioantimonate(V)families,and also indicates that the cation size effect introduced by elemental substitution may lead to surprising performance improvements.
