One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,...One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.展开更多
A new coordination compound, [Co（L223）2（H2O）2]·H2pm（1, L223 = 3,4-bis（2-pyridyl）-5-（3-pyridyl）-1,2,4-triazole and H4 pm = pyromellitic acid）, has been synthesized. The structure of complex 1 has been ch...A new coordination compound, [Co（L223）2（H2O）2]·H2pm（1, L223 = 3,4-bis（2-pyridyl）-5-（3-pyridyl）-1,2,4-triazole and H4 pm = pyromellitic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the triclinic system, space group P1 with a = 10.2470（8）, b = 10.2879（9）, c = 10.2951（11） ？, α = 109.398（2）, β = 97.6590（10）, γ = 95.3260（10）°, V = 1003.60（16） ？3, Z = 1, Dc = 1.565 g/cm^3, μ = 0.508 mm%^-1, Mr = 945.73, F（000） = 485, the final R = 0.0562 and w R = 0.0783 with I 〉 2σ（I）. Two L223 as chelating ligands link one Co（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 2D coordination pattern with hydrogen bonds. In addition, the antifungal effects of the ligand and the complex were evaluated by the disc diffusion method against Colletotrichum gloeosporioides Penz. 1 represents antifungal activity with high levels of inhibitory potency which is larger than the corresponding ligand.展开更多
A new coordination compound Zn（2,4＇-bpt）2（H2O）（1） based on the versatile ligand 2,4＇-Hbpt（2,4？-Hbpt = 3-（2-pyridyl）-5-（4-pyridyl）-1H-1,2,4-triazole） was prepared by hydrothermal reactions. The structure...A new coordination compound Zn（2,4＇-bpt）2（H2O）（1） based on the versatile ligand 2,4＇-Hbpt（2,4？-Hbpt = 3-（2-pyridyl）-5-（4-pyridyl）-1H-1,2,4-triazole） was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877（3）, b = 0.7483（9）, c = 1.2492（2） A, b = 92.681（2）°, V = 2230.6（4） A^3, Z = 4, Dc = 1.572 g/cm^3, m = 1.143 mm^-1, Mr = 527.85 and F（000） = 1080. The final R = 0.0581 and wR = 0.0898 with I 〉 2s（I）. 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory（DFT） were employed in order to explicate the stability and chemical reactivity of 2,4＇-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.展开更多
Bimetallic clusters have aroused tremendous interest because the property changes like structure,size,and composition have occurred.Herein,a structural search of the global minimum for anionic LiMg_(n)^(-)(n=2-11) clu...Bimetallic clusters have aroused tremendous interest because the property changes like structure,size,and composition have occurred.Herein,a structural search of the global minimum for anionic LiMg_(n)^(-)(n=2-11) clusters is performed using an efficient crystal structure analysis by particle swarm optimization(CALYPSO) structural searching program with subsequent density functional theory(DFT) calculations.A great variety of low energetic isomers are converged,and the most stable ones are confirmed by comparing their total energy of each size.It is found that the LiMg_(n)^(-)clusters are structurally consistent with corresponding Mg clusters anions except for LiMg_(5)^(-)and LiMg_(7)^(-).In all the doped clusters,the Li atom prefers to occupy the convex position.Simulated photoelectron spectra(PES),Infrared(IR),and Raman spectra of LiMg_(n)^(-)could be used as an essential evidence for identifying cluster structures experimentally in the future.Stability study reveals that a tower-like structure of LiMg_(9)^(-)has prominent stability and can be identified as a magic number cluster.The reason might be that there are both closed-shell 1S^(2)1P^(6)1D^(10)2S^(2) electronic configurations and stronger Li-Mg bonds caused by sp hybridization in the LiMg_(9)^(-)cluster.展开更多
The band gap structures by arranging hybrid shunted piezoelectric materialswith resistance inductive （RL） circuit and negative impedance converter （NIC） closely and at in- tervals are presented. The theoretical mo...The band gap structures by arranging hybrid shunted piezoelectric materialswith resistance inductive （RL） circuit and negative impedance converter （NIC） closely and at in- tervals are presented. The theoretical model is built using transfer matrix method. Then the MATLAB computing language is utilized to simulate the band gap structures. Meanwhile, the effects of the resistance, inductance and capacitance on the local resonant gap are studied. By comparing different combinations of resistance, inductance and capacitance as well as different arrangement of circuits, a 13 kHz band gap is reached under the effect of arranging hybrid pe- riodic shunted piezoelectric patches at intervals and the stability of the system is also analyzed. It is proved that utilizing hybrid shunted piezoelectric patches would have a clear impact on the band gap structure of phononic crystal rods. Moreover, the band gap would be clearly enlarged by arranging hybrid piezoelectric patches at intervals.展开更多
Inorganic solid electrolytes have obvious advantages on safety and electrochemical stability compared to organic liquid electrolytes,but the advance on high ionic conductivity of typical electrolytes is still undergoi...Inorganic solid electrolytes have obvious advantages on safety and electrochemical stability compared to organic liquid electrolytes,but the advance on high ionic conductivity of typical electrolytes is still undergoing.Although the first-principles calculation in the ion migration simulation is an important strategy to develop high-performance solid electrolyte,the process is very time-consuming.Here,we propose an effective method by combining the geometrical analysis and bond valance sum calculation to obtain an approximate minimum energy path preliminarily,in parallel to pave the way for the interoperability of low-precision and high-precision ion transport calculation.Taking a promising electrolyte Li_(3)PS_(4) as an example,we revisit its Li-ionic transport behavior.Our calculated Li-ion pathways and the activation energies(the corresponding values:1.09 eV vs.0.88 eV vs.0.86 eV)in γ-,β- and α-Li_(3)PS_(4) are consistent with the ones obtained from the first-principles calculations.The variations of the position of P-ions lead the rearrangement of the host PS_(4) tetrahedron,affecting the diffusion positions of Li-ions and further enabling high Li^(+) conductivity in β-Li_(3)PS_(4).展开更多
Nonlinear optical(NLO)crystals can expand the wavelength of coherent light by frequency conversion,and thus have significant applications in modern lasers,semiconductor manufacturing and lithography.However,the target...Nonlinear optical(NLO)crystals can expand the wavelength of coherent light by frequency conversion,and thus have significant applications in modern lasers,semiconductor manufacturing and lithography.However,the targeted synthesis of high-performance NLO crystals remains an ongoing challenge.Herein,two stable strong NLO crystals,(A_(2)I)[PbI(OOC(CH_(2))_(2)COO)](A=Rb,K),have been rationally obtained through a convenient mixed solvothermal method.The highly distorted[PbI_(2)O_(4)]polyhedra which show large hyperpolarizability and polarizability anisotropy adopt an oriented arrangement that enables favourable superposition of their microscopic second-order susceptibilities.Remarkably,(A_(2)I)[PbI(OOC(CH_(2))_(2)COO)](A=Rb,K)not only exhibit strong phase-matching SHG response(7.3 and 5.8×KDP)and large birefringence(0.205 and 0.245@1064 nm),but also present high thermal stability up to 250℃ in air and good crystal growth habit.Based on theoretical calculations and structural analysis,their strong SHG response predominantly originated from the distorted[PbI_(2)O_(4)]polyhedra.This study provides an efficient approach for the future discovery of new high-performance NLO crystals.展开更多
Here we report on one-dimensional nano objects of formula[Yb(hfac)_(3)(M-or P-Ant-C8)]_(n) where the Ant-C8 moiety refers to enantiopure M-and P-twistacenes decorated at positions 2,6 with 4-pyridyl-ethynyl units and ...Here we report on one-dimensional nano objects of formula[Yb(hfac)_(3)(M-or P-Ant-C8)]_(n) where the Ant-C8 moiety refers to enantiopure M-and P-twistacenes decorated at positions 2,6 with 4-pyridyl-ethynyl units and helically locked into an end-to-end twist by an octyl tether.The crystal structure analysis reveals intertwined 1D nano-chains featuring two crystallographically independent Yb(III)ions.Under applied magnetic fields these systems show slow relaxation of the magnetization.The optical properties show the expected contributions of the ^(2)F_(7/2)←^(2)F_(5/2) electronic transition of the Yb(III)ions split by the crystal field.Magnetic field and temperature dependent Magneto-Chiral Dichroism(MChD)studies reveal contributions of opposite sign and similar intensity for the two crystallographically independent ions that cancel out for the 0-0′and 0-2′absorptions but not for the 0-1′.These findings,supported by ab intio theoretical calculations,demonstrate the important role of the structural arrangement of MChD-active ions when designing chiral magneto-optical materials responsive to light and magnetic fields.展开更多
Two novel ionic liquids,[Bzmim]Cl and[Bzmim][AuCl_(4)],were successfully synthesized and characterized by ^(1)H NMR spectroscopy,single crystal structure analysis and quantum mechanical calculations.Meanwhile,multiple...Two novel ionic liquids,[Bzmim]Cl and[Bzmim][AuCl_(4)],were successfully synthesized and characterized by ^(1)H NMR spectroscopy,single crystal structure analysis and quantum mechanical calculations.Meanwhile,multiple supramolecular interactions of[Bzmim][AuCl_(4)](hydrogen bonds,Cl…π,Au…π interactions and π-π stacking)were found between the N-methylimidazolium cation and AuCl_(4)^(-).Interestingly,the interactions made it easy for[Bzmim][AuCl_(4)]to form a 3D supramolecular structure.Thus,a series of N-methylimidazolium-based poly(ionic liquids)were synthesized to recover Au(Ⅲ)in aqueous solution.They show high adsorption capacity and excellent selectivity for tetrachloroaurate anions which can be used as solid phase extraction agents over a wide temperature range.Notably,the acid thiourea can desorb Au(Ⅲ)from polymeric ionic liquids(PILs),thus they also exhibit excellent recyclability.Among them,PS-b-PVBnMeImCl-5.9 has the highest efficiency for Au(Ⅲ)recovery after five adsorption-desorption cycles.Compared with the Raman spectroscopy results of gold-containing PS-b-PVBnMeImCl-5.9,1H NMR of[Bzmim][AuCl4]revealed that the Au(Ⅲ)recovery mechanism by polymeric ionic liquids was due to a combination of electrostatic interactions and multiple weak intermolecular interactions.展开更多
An organic-inorganic semiconducting compound of 1-methylpiperidinium triiodoplumbate(Ⅱ)(MPIP),adopting a one-dimensional ABX3 perovskite-like structure,has been synthesized.It is notable that MPIP undergoes a structu...An organic-inorganic semiconducting compound of 1-methylpiperidinium triiodoplumbate(Ⅱ)(MPIP),adopting a one-dimensional ABX3 perovskite-like structure,has been synthesized.It is notable that MPIP undergoes a structural phase transition(SPT)at T_(c)≌202 K,as confirmed by DSC and C_(p) analyses.Strikingly,MPIP exhibits remarkable switchable dielectric responses;that is,the distinct step-like anomalies in the vicinity of T_(c).The switching between high-dielectric and low-dielectric states makes MPIP a potential switchable dielectric material.Single-crystal structural analysis reveals that the most distinct difference between its high-temperature phase(above T_(c))and low-temperature phase(below T_(c))is the order-disorder transformation of a 1-methylpiperidinium cation,which accounts for its SPT and striking dielectric response.Besides this,MPIP shows semiconducting behaviour with an optical bandgap of ~2.48 eV,comparable to some other lead-iodide perovskites.The combination of semiconducting and dielectric attributes provides a new perspective for the design of hybrid perovskites as multifunctional materials.展开更多
A series of manganese(II)complexes supported by cyclopentadienyl-phosphine ligands have been synthesized and characterized.A reaction of potassium salts of a cyclopentadienyl-phosphine ligand(LK)with MnX_(2) provided ...A series of manganese(II)complexes supported by cyclopentadienyl-phosphine ligands have been synthesized and characterized.A reaction of potassium salts of a cyclopentadienyl-phosphine ligand(LK)with MnX_(2) provided dimeric complexes[LMn(μ-X)]_(2)(X=Cl,1a;X=Br,1b)in high yields.The monomeric complex[K(18-crown-6)][LMnCl_(2)](2)was obtained with the addition of 18-crown-6.[LMn(μ-Cl)]_(2)(1a)served as a precursor to dimeric amido and methyl manganese(II)complexes including[LMn(μ-NH_(2))]_(2)(3)and[LMn(μ-Me)]_(2)(4).Treatment of[LMn(μ-Cl)]_(2)(1a)with EtMgCl,PhMgBr or other reductants resulted in the formation of sandwich manganese(II)complex L_(2)Mn(5).Complexes 1a,b,2-5 were characterized by a single-crystal X-ray structural analysis.展开更多
基金Supported by the financial support of Fundamental Research Funds for the Central Universities(3207045420)Jiangsu Ainaji Neoenergy Science&Technology Co.,Ltd.(8507040091)
文摘One new polymer [Co（L）（H2O）2]n（1） was synthesized by 4-（ethoxycarbonyl）-5-methyl-1H-1,2,3-triazole-1-carboxylic acid（Emtc） under the in situ solvent thermal reaction（H2L = 1-（carboxymethyl）-5-methyl-1H-1,2,3-triazole-4-carboxylic acid）. The title complex performs a wave-like 2D framework and the ligand H2L demonstrates the coordination mode as μ4-η-2：η-1η-1：η-1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.
基金Supported by the Natural Science Foundation of Ningxia(No.NZ15015)
文摘A new coordination compound, [Co（L223）2（H2O）2]·H2pm（1, L223 = 3,4-bis（2-pyridyl）-5-（3-pyridyl）-1,2,4-triazole and H4 pm = pyromellitic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the triclinic system, space group P1 with a = 10.2470（8）, b = 10.2879（9）, c = 10.2951（11） ？, α = 109.398（2）, β = 97.6590（10）, γ = 95.3260（10）°, V = 1003.60（16） ？3, Z = 1, Dc = 1.565 g/cm^3, μ = 0.508 mm%^-1, Mr = 945.73, F（000） = 485, the final R = 0.0562 and w R = 0.0783 with I 〉 2σ（I）. Two L223 as chelating ligands link one Co（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 2D coordination pattern with hydrogen bonds. In addition, the antifungal effects of the ligand and the complex were evaluated by the disc diffusion method against Colletotrichum gloeosporioides Penz. 1 represents antifungal activity with high levels of inhibitory potency which is larger than the corresponding ligand.
基金Supported by the National Natural Science Foundation of China(Nos.21263019 and 51364038)
文摘A new coordination compound Zn（2,4＇-bpt）2（H2O）（1） based on the versatile ligand 2,4＇-Hbpt（2,4？-Hbpt = 3-（2-pyridyl）-5-（4-pyridyl）-1H-1,2,4-triazole） was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877（3）, b = 0.7483（9）, c = 1.2492（2） A, b = 92.681（2）°, V = 2230.6（4） A^3, Z = 4, Dc = 1.572 g/cm^3, m = 1.143 mm^-1, Mr = 527.85 and F（000） = 1080. The final R = 0.0581 and wR = 0.0898 with I 〉 2s（I）. 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory（DFT） were employed in order to explicate the stability and chemical reactivity of 2,4＇-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.
基金Project supported by the National Natural Science Foundation of China(Grant No.11404008)the Innovation Training Program for College Students of Shanxi Province of China(Grant No.S201910721061)the Innovation Training Program for College Students of Baoji University of Arts and Sciences(Grant No.20191XJ087)。
文摘Bimetallic clusters have aroused tremendous interest because the property changes like structure,size,and composition have occurred.Herein,a structural search of the global minimum for anionic LiMg_(n)^(-)(n=2-11) clusters is performed using an efficient crystal structure analysis by particle swarm optimization(CALYPSO) structural searching program with subsequent density functional theory(DFT) calculations.A great variety of low energetic isomers are converged,and the most stable ones are confirmed by comparing their total energy of each size.It is found that the LiMg_(n)^(-)clusters are structurally consistent with corresponding Mg clusters anions except for LiMg_(5)^(-)and LiMg_(7)^(-).In all the doped clusters,the Li atom prefers to occupy the convex position.Simulated photoelectron spectra(PES),Infrared(IR),and Raman spectra of LiMg_(n)^(-)could be used as an essential evidence for identifying cluster structures experimentally in the future.Stability study reveals that a tower-like structure of LiMg_(9)^(-)has prominent stability and can be identified as a magic number cluster.The reason might be that there are both closed-shell 1S^(2)1P^(6)1D^(10)2S^(2) electronic configurations and stronger Li-Mg bonds caused by sp hybridization in the LiMg_(9)^(-)cluster.
基金supported by the National Natural Science Foundation of China(11202056)the Fundamental Research Funds for the Central Universities(HEUCFQ20150305)
文摘The band gap structures by arranging hybrid shunted piezoelectric materialswith resistance inductive （RL） circuit and negative impedance converter （NIC） closely and at in- tervals are presented. The theoretical model is built using transfer matrix method. Then the MATLAB computing language is utilized to simulate the band gap structures. Meanwhile, the effects of the resistance, inductance and capacitance on the local resonant gap are studied. By comparing different combinations of resistance, inductance and capacitance as well as different arrangement of circuits, a 13 kHz band gap is reached under the effect of arranging hybrid pe- riodic shunted piezoelectric patches at intervals and the stability of the system is also analyzed. It is proved that utilizing hybrid shunted piezoelectric patches would have a clear impact on the band gap structure of phononic crystal rods. Moreover, the band gap would be clearly enlarged by arranging hybrid piezoelectric patches at intervals.
基金supported by the National Key Research and Development Program of China(Nos.2017YFB0701600)the National Natural Science Foundation of China(51622207,U1630134).
文摘Inorganic solid electrolytes have obvious advantages on safety and electrochemical stability compared to organic liquid electrolytes,but the advance on high ionic conductivity of typical electrolytes is still undergoing.Although the first-principles calculation in the ion migration simulation is an important strategy to develop high-performance solid electrolyte,the process is very time-consuming.Here,we propose an effective method by combining the geometrical analysis and bond valance sum calculation to obtain an approximate minimum energy path preliminarily,in parallel to pave the way for the interoperability of low-precision and high-precision ion transport calculation.Taking a promising electrolyte Li_(3)PS_(4) as an example,we revisit its Li-ionic transport behavior.Our calculated Li-ion pathways and the activation energies(the corresponding values:1.09 eV vs.0.88 eV vs.0.86 eV)in γ-,β- and α-Li_(3)PS_(4) are consistent with the ones obtained from the first-principles calculations.The variations of the position of P-ions lead the rearrangement of the host PS_(4) tetrahedron,affecting the diffusion positions of Li-ions and further enabling high Li^(+) conductivity in β-Li_(3)PS_(4).
基金supported by the National Natural Science Foundation of China(No.22275184,22278031)the Natural Science Foundation of Yantai(No.2024JCYJ065).
文摘Nonlinear optical(NLO)crystals can expand the wavelength of coherent light by frequency conversion,and thus have significant applications in modern lasers,semiconductor manufacturing and lithography.However,the targeted synthesis of high-performance NLO crystals remains an ongoing challenge.Herein,two stable strong NLO crystals,(A_(2)I)[PbI(OOC(CH_(2))_(2)COO)](A=Rb,K),have been rationally obtained through a convenient mixed solvothermal method.The highly distorted[PbI_(2)O_(4)]polyhedra which show large hyperpolarizability and polarizability anisotropy adopt an oriented arrangement that enables favourable superposition of their microscopic second-order susceptibilities.Remarkably,(A_(2)I)[PbI(OOC(CH_(2))_(2)COO)](A=Rb,K)not only exhibit strong phase-matching SHG response(7.3 and 5.8×KDP)and large birefringence(0.205 and 0.245@1064 nm),but also present high thermal stability up to 250℃ in air and good crystal growth habit.Based on theoretical calculations and structural analysis,their strong SHG response predominantly originated from the distorted[PbI_(2)O_(4)]polyhedra.This study provides an efficient approach for the future discovery of new high-performance NLO crystals.
基金The French National Research Agency(ANR)is acknowledged for financial support through the SWITCH-MChD(ANR-23-CE07-0003)PRINCIPE(ANR-23-CE07-0015)projects+2 种基金This project has received financial support from the CNRS through the MITI interdisciplinary programs through its exploratory research programThe French GENCI/IDRIS-CINES centers for high-performance computing resources are also acknowledged.O.G.acknowledges European Union's Horizon 2020 research and innovation program(grant agreement no.850836,ERC Starting Grant“PolyHelix”)the Israel Science Foundation(grant no.3085/21).
文摘Here we report on one-dimensional nano objects of formula[Yb(hfac)_(3)(M-or P-Ant-C8)]_(n) where the Ant-C8 moiety refers to enantiopure M-and P-twistacenes decorated at positions 2,6 with 4-pyridyl-ethynyl units and helically locked into an end-to-end twist by an octyl tether.The crystal structure analysis reveals intertwined 1D nano-chains featuring two crystallographically independent Yb(III)ions.Under applied magnetic fields these systems show slow relaxation of the magnetization.The optical properties show the expected contributions of the ^(2)F_(7/2)←^(2)F_(5/2) electronic transition of the Yb(III)ions split by the crystal field.Magnetic field and temperature dependent Magneto-Chiral Dichroism(MChD)studies reveal contributions of opposite sign and similar intensity for the two crystallographically independent ions that cancel out for the 0-0′and 0-2′absorptions but not for the 0-1′.These findings,supported by ab intio theoretical calculations,demonstrate the important role of the structural arrangement of MChD-active ions when designing chiral magneto-optical materials responsive to light and magnetic fields.
基金supported by the National Natural Science Foundation of China(Grant 51474118).
文摘Two novel ionic liquids,[Bzmim]Cl and[Bzmim][AuCl_(4)],were successfully synthesized and characterized by ^(1)H NMR spectroscopy,single crystal structure analysis and quantum mechanical calculations.Meanwhile,multiple supramolecular interactions of[Bzmim][AuCl_(4)](hydrogen bonds,Cl…π,Au…π interactions and π-π stacking)were found between the N-methylimidazolium cation and AuCl_(4)^(-).Interestingly,the interactions made it easy for[Bzmim][AuCl_(4)]to form a 3D supramolecular structure.Thus,a series of N-methylimidazolium-based poly(ionic liquids)were synthesized to recover Au(Ⅲ)in aqueous solution.They show high adsorption capacity and excellent selectivity for tetrachloroaurate anions which can be used as solid phase extraction agents over a wide temperature range.Notably,the acid thiourea can desorb Au(Ⅲ)from polymeric ionic liquids(PILs),thus they also exhibit excellent recyclability.Among them,PS-b-PVBnMeImCl-5.9 has the highest efficiency for Au(Ⅲ)recovery after five adsorption-desorption cycles.Compared with the Raman spectroscopy results of gold-containing PS-b-PVBnMeImCl-5.9,1H NMR of[Bzmim][AuCl4]revealed that the Au(Ⅲ)recovery mechanism by polymeric ionic liquids was due to a combination of electrostatic interactions and multiple weak intermolecular interactions.
基金the CAS-TWAS President program of the UCAS for financial supportsupported by the NSFC(21622108,21525104,21601188,91422301,21571178,51502288 and 51502290)+2 种基金the Strategic Priority Research Program of the CAS(XDB20000000)the Youth Innovation Promotion of CAS(2014262)the support from the State Key Laboratory of Luminescence and Applications(SKLA-2016-09).
文摘An organic-inorganic semiconducting compound of 1-methylpiperidinium triiodoplumbate(Ⅱ)(MPIP),adopting a one-dimensional ABX3 perovskite-like structure,has been synthesized.It is notable that MPIP undergoes a structural phase transition(SPT)at T_(c)≌202 K,as confirmed by DSC and C_(p) analyses.Strikingly,MPIP exhibits remarkable switchable dielectric responses;that is,the distinct step-like anomalies in the vicinity of T_(c).The switching between high-dielectric and low-dielectric states makes MPIP a potential switchable dielectric material.Single-crystal structural analysis reveals that the most distinct difference between its high-temperature phase(above T_(c))and low-temperature phase(below T_(c))is the order-disorder transformation of a 1-methylpiperidinium cation,which accounts for its SPT and striking dielectric response.Besides this,MPIP shows semiconducting behaviour with an optical bandgap of ~2.48 eV,comparable to some other lead-iodide perovskites.The combination of semiconducting and dielectric attributes provides a new perspective for the design of hybrid perovskites as multifunctional materials.
基金supported by the National Natural Science Foundation of China(No.21690061 and 21725201).
文摘A series of manganese(II)complexes supported by cyclopentadienyl-phosphine ligands have been synthesized and characterized.A reaction of potassium salts of a cyclopentadienyl-phosphine ligand(LK)with MnX_(2) provided dimeric complexes[LMn(μ-X)]_(2)(X=Cl,1a;X=Br,1b)in high yields.The monomeric complex[K(18-crown-6)][LMnCl_(2)](2)was obtained with the addition of 18-crown-6.[LMn(μ-Cl)]_(2)(1a)served as a precursor to dimeric amido and methyl manganese(II)complexes including[LMn(μ-NH_(2))]_(2)(3)and[LMn(μ-Me)]_(2)(4).Treatment of[LMn(μ-Cl)]_(2)(1a)with EtMgCl,PhMgBr or other reductants resulted in the formation of sandwich manganese(II)complex L_(2)Mn(5).Complexes 1a,b,2-5 were characterized by a single-crystal X-ray structural analysis.
