Two new thioantimonates,(NH4)2Sb10S16(1)and K1.4(NH4)0.6Sb10S16(2),have been synthesized by solvothermal method with the yields of 80%and 85%,respectively.Single-crystal X-ray diffraction(SCXRD)study reveals that 1 cr...Two new thioantimonates,(NH4)2Sb10S16(1)and K1.4(NH4)0.6Sb10S16(2),have been synthesized by solvothermal method with the yields of 80%and 85%,respectively.Single-crystal X-ray diffraction(SCXRD)study reveals that 1 crystallizes in the monoclinic space group of Pn with a=8.1284(4),b=19.4587(9),c=9.1030(4)A,β=91.736(5)°,V=1439.14(12)A^(3),Z=2,Dc=4.077 g·cm^(-3),F(000)=1576,μ=10.389 mm^(-1),R=0.0343 and w R=0.0624(I>2σ(I));2 also crystallizes in the monoclinic space group of Pn with a=8.0989(6),b=19.3730(17),c=9.0411(6)A,β=91.879(6)°,V=1417.79(19)A^(3),Z=2,Dc=4.207 g·cm^(-3),F(000)=1598,μ=10.748 mm-1,R=0.0323 and w R=0.0664(I>2σ(I)).The anionic frameworks of two compounds both feature two-dimensional(2D)[Sb10S16]n2n-layers.The stabilities and optoelectronic properties of 1 and 2 have been characterized.In particular,they are stable under acidic or alkaline conditions(pH=0 or 12.5),showing excellent acid-based resistance.展开更多
An inorganic-organic hybrid thioantimonate（Ⅲ） [CH3（CH2）3NH3]2Sb4S7 1 with layered structure was synthesized by solvothermal method. 1 crystallizes in the triclinic system, space group P1 with a = 7.0124（11）, b ...An inorganic-organic hybrid thioantimonate（Ⅲ） [CH3（CH2）3NH3]2Sb4S7 1 with layered structure was synthesized by solvothermal method. 1 crystallizes in the triclinic system, space group P1 with a = 7.0124（11）, b = 11.919（2）, c =14.879（3）A, α = 108.791（3）, β= 102.441（3）, γ = 92.846（2）°, V= 1140.1（3）A3, Mr = 859.71, Z= 2, Do = 2.504 g/cm^3 ,μ = 5.324 mm^-1, F（000） = 804, S = 1.013, the Final R = 0.0297 and wR = 0.0618 for 3534 observed reflections with Ⅰ 〉 2 σ（Ⅰ）. 1 consists of [C4HgNH3]＋ cations and two-dimensional [Sb4ST]n^2n- anion which is composed of three SbS3 trigonal pyranaids and one SbS4 unit joined by sharing common comers. The anionic layers are stacked perpendicularly to the c axis of the unit cell forming two-dimensional channels between the layers. The [C4H9NH3]^＋ cations interdigitate in a bilayer and reside in the 2D channels leading to a sandwich-like arrangement of the anion and cations.展开更多
A new inorganic-organic hybrid lanthannm thioantimonate（V） with bidentate and tetradentate mixed amino ligands, namely La（teta）（en）（μ-η1,η2-SbS4） （1, teta = triethylenetetramine, en = ethylenediamine）, ha...A new inorganic-organic hybrid lanthannm thioantimonate（V） with bidentate and tetradentate mixed amino ligands, namely La（teta）（en）（μ-η1,η2-SbS4） （1, teta = triethylenetetramine, en = ethylenediamine）, has been solvothermally synthesized and structurally, thermally and optically characterized. In 1, the en ligand is in situ produced by re-aggregation of teta which plays multiple roles in the reaction as ligand, reactive solvent and precursor. Single-crystal X-ray analysis reveals that 1 belongs to the orthorhombic space group P212121. Its structure features a one-dimensional organic-inorganic hybrid chain of [La（teta）（en）（μ-η1,η2-SbS4）],, constructed by alternating arrangement of μ-η1,η2-sbvs4 tetrahedron and La（teta）（en） complex. Keywords： thioantimonate, lanthanum, amino ligand, crystal structure, optical property展开更多
Exploring inorganic materials with two or more different physical properties has become an important and emerging topic in solid-state chemistry.Despite the considerable progress achieved recently,however,multifunctio...Exploring inorganic materials with two or more different physical properties has become an important and emerging topic in solid-state chemistry.Despite the considerable progress achieved recently,however,multifunctional infrared nonlinear-optical(IR-NLO)chalcogenides are still rarely reported.This paper is the first report of quaternary manganese thioantimonates,A_(3)Mn_(2)Sb_(3)S_(8)(A=K and Rb),developed using a facile surfactant–thermal method.Both compounds are isostructural and belong to the tetragonal space group I4¯2m(no.121).Their structures are composed of unique three-dimensional non-centrosymmetric[Mn_(2)Sb_(3)S_(8)]^(3−)frameworks and intervening alkali A+cations.Significantly,A_(3)Mn_(2)Sb_(3)S_(8)(A=K and Rb)not only show type-I phase-matching features with moderate second-harmonic generation(SHG)effects and strong laser-induced damage thresholds but also display temperature-dependent paramagnetism and photocurrent responses.In addition,the highly polarizable[Sb_(3)S_(7)]^(5−)group in this type of structure is a beneficial NLO-active motif,which can be instrumental in designing new IR-NLO materials with suitable birefringence and strong SHG efficiency based on the experimental and theoretical research results.This study will contribute to enrich the diversity of lone-pair cation-based NLO-active units and open a new avenue for discovering other multifunctional IR-NLO materials.展开更多
With ammonium ions as structure-directing agents,two novel silver thioantimonates (NH_(4))AgSb4S7·H_(2)O (1) and (NH_(4))AgSb2S4 (2) have been surfactant-thermally synthesized and fully characterized. Compound 1 ...With ammonium ions as structure-directing agents,two novel silver thioantimonates (NH_(4))AgSb4S7·H_(2)O (1) and (NH_(4))AgSb2S4 (2) have been surfactant-thermally synthesized and fully characterized. Compound 1 features a three dimensional (3D) open framework while compound 2 possesses a two dimensional (2D) layer structure. The optical band gaps are estimated to be 1.70 eV for 1 and 1.84 eV for 2,exhibiting semiconductor properties for visible light absorption. The photocatalytic experiments demonstrated that both 1 and 2 were able to degrade crystal violet (CV) and rhodamine B (RhB) under visible light irradiation. Moreover,compounds 1 and 2 also displayed selective photocatalytic abilities in CV degradation.展开更多
It is an important and challenging task to develop new infrared(IR)birefringent materials to promote the development of laser technology.In this work,a novel thioantimonate with the highest Cu-to-Sb ratio in the quate...It is an important and challenging task to develop new infrared(IR)birefringent materials to promote the development of laser technology.In this work,a novel thioantimonate with the highest Cu-to-Sb ratio in the quaternary X/Cu/Sb/Q(X=cations;Q=chalcogen)system,namely CsCu_(3)SbS_(4),was structurally designed and prepared by the strategy of alkali metal introduction into known Cu_(3)SbS_(4).Interestingly,CsCu_(3)SbS_(4)has novel two-dimensional anionic[Cu_(3)SbS_(4)]^(−)layers formed by the unprecedented onedimensional[Cu_(3)S_(3)S_(3/2)]^(6−)chains and discrete[SbS_(3)]_(3)−clusters.Meanwhile,compared with the prototype Cu_(3)SbS_(4),CsCu_(3)SbS_(4)realizes an enormous birefringence boost from 0 to 0.232,which was confirmed by both experimental results and theoretical calculations.This study enriches the sources of thioantimonates and sheds more light on the structure–property relationships of IR birefringent materials.展开更多
Rechargeable lithium-ion batteries(LIBs)have attracted great attention in various applications.However,high energy density is still a challenge for next-generation lithium ion batteries.Therefore,searching for novel e...Rechargeable lithium-ion batteries(LIBs)have attracted great attention in various applications.However,high energy density is still a challenge for next-generation lithium ion batteries.Therefore,searching for novel electrode materials to address this issue is highly desirable.In this report,we employed a surfactant-thermal method to prepare a novel 1D crystalline thioantimonate[NH(CH_(3))_(2)][Sb_(4)S_(5)(S_(3))].After grinding for 10 min using a mortar,[NH(CH_(3))_(2)][Sb_(4)S_(5)(S_(3))]presented an ultrathin nanosheet morphology(around 20 nm in thickness and several micrometers in lateral dimension).Employed as an anode material for lithium ion batteries,the nano-sized crystalline thioantimonate shows a high reversible specific capacity of 568 mA h g^(−1)over 50 cycles at a current density of 0.1 A g^(−1)and an excellent rate capability of 301 mA h g^(−1)at a current density of 5 A g^(−1).Our research suggests that crystalline thioantimonate could have great potential applications in high performance Li-ion batteries.展开更多
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 National Science Foundations of China(Nos.22076185 and 21771183)the Natural Science Foundation of Fujian Province(No.2020J06033)FJIRSM&IUE Joint Research Fund(No.RHZX-2018-005)。
文摘Two new thioantimonates,(NH4)2Sb10S16(1)and K1.4(NH4)0.6Sb10S16(2),have been synthesized by solvothermal method with the yields of 80%and 85%,respectively.Single-crystal X-ray diffraction(SCXRD)study reveals that 1 crystallizes in the monoclinic space group of Pn with a=8.1284(4),b=19.4587(9),c=9.1030(4)A,β=91.736(5)°,V=1439.14(12)A^(3),Z=2,Dc=4.077 g·cm^(-3),F(000)=1576,μ=10.389 mm^(-1),R=0.0343 and w R=0.0624(I>2σ(I));2 also crystallizes in the monoclinic space group of Pn with a=8.0989(6),b=19.3730(17),c=9.0411(6)A,β=91.879(6)°,V=1417.79(19)A^(3),Z=2,Dc=4.207 g·cm^(-3),F(000)=1598,μ=10.748 mm-1,R=0.0323 and w R=0.0664(I>2σ(I)).The anionic frameworks of two compounds both feature two-dimensional(2D)[Sb10S16]n2n-layers.The stabilities and optoelectronic properties of 1 and 2 have been characterized.In particular,they are stable under acidic or alkaline conditions(pH=0 or 12.5),showing excellent acid-based resistance.
基金the Natural Science Foundation of Universities of Jiangsu Province (No. 05KJB150110)
文摘An inorganic-organic hybrid thioantimonate（Ⅲ） [CH3（CH2）3NH3]2Sb4S7 1 with layered structure was synthesized by solvothermal method. 1 crystallizes in the triclinic system, space group P1 with a = 7.0124（11）, b = 11.919（2）, c =14.879（3）A, α = 108.791（3）, β= 102.441（3）, γ = 92.846（2）°, V= 1140.1（3）A3, Mr = 859.71, Z= 2, Do = 2.504 g/cm^3 ,μ = 5.324 mm^-1, F（000） = 804, S = 1.013, the Final R = 0.0297 and wR = 0.0618 for 3534 observed reflections with Ⅰ 〉 2 σ（Ⅰ）. 1 consists of [C4HgNH3]＋ cations and two-dimensional [Sb4ST]n^2n- anion which is composed of three SbS3 trigonal pyranaids and one SbS4 unit joined by sharing common comers. The anionic layers are stacked perpendicularly to the c axis of the unit cell forming two-dimensional channels between the layers. The [C4H9NH3]^＋ cations interdigitate in a bilayer and reside in the 2D channels leading to a sandwich-like arrangement of the anion and cations.
基金supported by the Knowledge Innovation Program of the Chinese Academy of Sciences(No.KJCX2-YW-H21)the NNSFC(Nos.20873149,20803081,and1001104)the NSF of Fujian Province(No.2008J0174 and 2010J01056)
文摘A new inorganic-organic hybrid lanthannm thioantimonate（V） with bidentate and tetradentate mixed amino ligands, namely La（teta）（en）（μ-η1,η2-SbS4） （1, teta = triethylenetetramine, en = ethylenediamine）, has been solvothermally synthesized and structurally, thermally and optically characterized. In 1, the en ligand is in situ produced by re-aggregation of teta which plays multiple roles in the reaction as ligand, reactive solvent and precursor. Single-crystal X-ray analysis reveals that 1 belongs to the orthorhombic space group P212121. Its structure features a one-dimensional organic-inorganic hybrid chain of [La（teta）（en）（μ-η1,η2-SbS4）],, constructed by alternating arrangement of μ-η1,η2-sbvs4 tetrahedron and La（teta）（en） complex. Keywords： thioantimonate, lanthanum, amino ligand, crystal structure, optical property
基金supported by the National Key R&D Program of China(2018YFB0605700)the National Natural Science Foundation of China(Nos.51778570,51879230,and 21771179)+1 种基金the Natural Science Foundation of Fujian Province(No.2019J01133)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR118).
文摘Exploring inorganic materials with two or more different physical properties has become an important and emerging topic in solid-state chemistry.Despite the considerable progress achieved recently,however,multifunctional infrared nonlinear-optical(IR-NLO)chalcogenides are still rarely reported.This paper is the first report of quaternary manganese thioantimonates,A_(3)Mn_(2)Sb_(3)S_(8)(A=K and Rb),developed using a facile surfactant–thermal method.Both compounds are isostructural and belong to the tetragonal space group I4¯2m(no.121).Their structures are composed of unique three-dimensional non-centrosymmetric[Mn_(2)Sb_(3)S_(8)]^(3−)frameworks and intervening alkali A+cations.Significantly,A_(3)Mn_(2)Sb_(3)S_(8)(A=K and Rb)not only show type-I phase-matching features with moderate second-harmonic generation(SHG)effects and strong laser-induced damage thresholds but also display temperature-dependent paramagnetism and photocurrent responses.In addition,the highly polarizable[Sb_(3)S_(7)]^(5−)group in this type of structure is a beneficial NLO-active motif,which can be instrumental in designing new IR-NLO materials with suitable birefringence and strong SHG efficiency based on the experimental and theoretical research results.This study will contribute to enrich the diversity of lone-pair cation-based NLO-active units and open a new avenue for discovering other multifunctional IR-NLO materials.
基金support from AcRF Tier 1(474,RG133/14 and RG 13/15)from MOE,Singapore.
文摘With ammonium ions as structure-directing agents,two novel silver thioantimonates (NH_(4))AgSb4S7·H_(2)O (1) and (NH_(4))AgSb2S4 (2) have been surfactant-thermally synthesized and fully characterized. Compound 1 features a three dimensional (3D) open framework while compound 2 possesses a two dimensional (2D) layer structure. The optical band gaps are estimated to be 1.70 eV for 1 and 1.84 eV for 2,exhibiting semiconductor properties for visible light absorption. The photocatalytic experiments demonstrated that both 1 and 2 were able to degrade crystal violet (CV) and rhodamine B (RhB) under visible light irradiation. Moreover,compounds 1 and 2 also displayed selective photocatalytic abilities in CV degradation.
基金supported by the National Natural Science Foundation of China(No.52171277,51778570,51879230,21771179,and 22175175)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR118)+2 种基金the Natural Science Foundation of Fujian Province(2019J01133)the Natural Science Basic Research Program of Shaanxi(2020JQ-710)the Doctoral Scientific Research Startup Foundation of Shaanxi University of Science and Technology(2018BJ-07).
文摘It is an important and challenging task to develop new infrared(IR)birefringent materials to promote the development of laser technology.In this work,a novel thioantimonate with the highest Cu-to-Sb ratio in the quaternary X/Cu/Sb/Q(X=cations;Q=chalcogen)system,namely CsCu_(3)SbS_(4),was structurally designed and prepared by the strategy of alkali metal introduction into known Cu_(3)SbS_(4).Interestingly,CsCu_(3)SbS_(4)has novel two-dimensional anionic[Cu_(3)SbS_(4)]^(−)layers formed by the unprecedented onedimensional[Cu_(3)S_(3)S_(3/2)]^(6−)chains and discrete[SbS_(3)]_(3)−clusters.Meanwhile,compared with the prototype Cu_(3)SbS_(4),CsCu_(3)SbS_(4)realizes an enormous birefringence boost from 0 to 0.232,which was confirmed by both experimental results and theoretical calculations.This study enriches the sources of thioantimonates and sheds more light on the structure–property relationships of IR birefringent materials.
基金financial support from AcRF Tier 1(RG 13/15 and RG133/14)Tier 2(ARC 20/12 and ARC 2/13)from MOE+1 种基金the CREATE program(Nanomaterials for Energy and Water Management)from NRF,Singaporesupport from Open Project of State Key Laboratory of Supramolecular Structure and Materials(Grant number:sklssm2015027),Jilin University,China.
文摘Rechargeable lithium-ion batteries(LIBs)have attracted great attention in various applications.However,high energy density is still a challenge for next-generation lithium ion batteries.Therefore,searching for novel electrode materials to address this issue is highly desirable.In this report,we employed a surfactant-thermal method to prepare a novel 1D crystalline thioantimonate[NH(CH_(3))_(2)][Sb_(4)S_(5)(S_(3))].After grinding for 10 min using a mortar,[NH(CH_(3))_(2)][Sb_(4)S_(5)(S_(3))]presented an ultrathin nanosheet morphology(around 20 nm in thickness and several micrometers in lateral dimension).Employed as an anode material for lithium ion batteries,the nano-sized crystalline thioantimonate shows a high reversible specific capacity of 568 mA h g^(−1)over 50 cycles at a current density of 0.1 A g^(−1)and an excellent rate capability of 301 mA h g^(−1)at a current density of 5 A g^(−1).Our research suggests that crystalline thioantimonate could have great potential applications in high performance Li-ion batteries.
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.
