Inorganic hole transport materials, particularly NiO_X, have shown considerable promise in boosting the efficiency and stability of perovskite solar cells. However, a major barrier to commercialization of NiO_X-based ...Inorganic hole transport materials, particularly NiO_X, have shown considerable promise in boosting the efficiency and stability of perovskite solar cells. However, a major barrier to commercialization of NiO_X-based perovskite solar cells with positive-intrinsic-negative architectures is their direct contact with the absorbing layer, which can lead to losses of photovoltage and fill factor. Furthermore, highly positive under-coordinated Ni cations degrade the perovskite at the interface. Here, we address these issues with the use of an ionic compound(QAPyBF_(4)) as an additive to passivate defects throughout the perovskite layer and improve carrier conduction and interactions with under-coordinated Ni cations. Specifically,the highly electronegative inorganic anion [BF_(4)]~- interacts with the NiO_x/perovskite interface to passivate under-coordinated cations(Ni^(≥3+)). Accordingly, the decorated cells achieved a power conversion efficiency of 23.38% and a fill factor of 85.5% without a complex surface treatment or NiO_X doping.展开更多
Decoupling electrical and thermal properties to enhance the figure of merit of thermoelectric materials underscores an in-depth understanding of the mechanisms that govern the transfer of charge carriers.Typically,a f...Decoupling electrical and thermal properties to enhance the figure of merit of thermoelectric materials underscores an in-depth understanding of the mechanisms that govern the transfer of charge carriers.Typically,a factor that contributes to the optimization of thermal conductivity is often found to be detrimental to the electrical transport properties.Here,we systematically investigated 26 dimeric MX_(2)-type compounds(where M represents a metal and X represents a nonmetal element)to explore the influence of the electronic configurations of metal cations on lattice thermal transport and thermoelectric performance using first-principles calculations.A principled scheme has been identified that the filled outer orbitals of the cation lead to a significantly lower lattice thermal conductivity compared to that of the partly occupied case for MX_(2),due to the much weakened bonds manifested by the shallow potential well,smaller interatomic force constants,and higher atomic displacement parameters.Based on these findings,we propose two ionic compounds,BaAs and BaSe_(2),to realize reasonable high electrical conductivities through the structural anisotropy caused by the inserted covalent X_(2) dimers while still maintaining the large lattice anharmonicity.The combined superior electrical and thermal properties of BaSe_(2) lead to a high n-type thermoelectric ZT value of 2.3 at 500 K.This work clarifies the structural origin of the heat transport properties of dimeric MX_(2)-type compounds and provides an insightful strategy for developing promising thermoelectric materials.展开更多
Switchable ionic compounds have wide applications in chemical processes.A switchable ionic compound based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU),CH_3OH and CO_2 was synthesized and characterized.DBU/CH_3OH/CO_2 ...Switchable ionic compounds have wide applications in chemical processes.A switchable ionic compound based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU),CH_3OH and CO_2 was synthesized and characterized.DBU/CH_3OH/CO_2 ionic compound was prepared in the presence of excess methanol,and then the excess methanol was removed by reduced pressure distillation in CO_2 atmosphere.The product yield(100%) reached the theoretical maximum for the first time.Its structure was identified by NMR,FT-IR,and XRD.The crystal product shows 8strong peaks in XRD at 2θ values of 16.0547°,16.4308°,16.7651°,18.8714°,19.2140°,21.9471°,22.0780°,and25.5661°.Its decomposition onset temperature(53 ℃) was affirmed by TGA,which is lower than its melting point.And its ionic switch point was measured by conductivity.展开更多
Interface engineering is an effective way to improve efficiency and long-term stability of perovskite solar cells(PSCs).Herein,an ionic compound tetrabutylammonium hexafluorophosphate(TP6)is adopted to passivate surfa...Interface engineering is an effective way to improve efficiency and long-term stability of perovskite solar cells(PSCs).Herein,an ionic compound tetrabutylammonium hexafluorophosphate(TP6)is adopted to passivate surface defects of the perovskite film.It is found that TP6 effectively reduced the surface defects,especially at the grain boundaries where the defects are abundant.Meanwhile,the exposed long alkyl chains and fluorine atoms in the TP6 enhanced the moisture stability of the perovskite film due to its strong hydrophobicity.In addition,the driving force of charge carrier separation and transport is increased by enlarged built-in potential.Consequently,the power conversion efficiency(PCE)of PSCs is significantly improved from 20.59% to 22.41%by increased open-circuit voltage(V_(oc))and fill factor(FF).The unencapsulated device with TP6 treatment exhibits better stability than the control device,and the PCE retains-80%of its initial PCE after 30 days under 15%-25%relative humidity in storage,while the PCE of the control device declines by more than 50%.展开更多
Room temperature ionic liquids(RTILs) are non-volatile organic salts. They may replace conventional coalescing agents in latex coating thus reducing volatile organic compounds(VOCs) emission as well as improving perfo...Room temperature ionic liquids(RTILs) are non-volatile organic salts. They may replace conventional coalescing agents in latex coating thus reducing volatile organic compounds(VOCs) emission as well as improving performance of latex coating products such as better thermal stability, conductivity, and antifouling property. The formation of latex coating containing RTILs can be achieved by encapsulation of RTILs inside particles via miniemulsion polymerization. In this study, the role of RTILs and its concentration on stability of miniemulsion during storage and polymerization were investigated. It has been found that, above a critical concentration(10 wt%), adding more RTILs to oil phase may weaken miniemulsion stability during storage as well as polymerization. Such observations were consistent with the zeta potential measurement for miniemulsions prepared at the similar conditions. The results obtained here would be a useful guideline for the development of new waterborne coating products with desirable functions and particle sizes.展开更多
A novel ionic compound [Fe（CN）6（phCH2NC5H5）3]·（H2O）4（Mr = 794.71） has been synthesized and its structure was characterized by IR, elemental analysis and X-my diffraction. The compound crystallizes in mono...A novel ionic compound [Fe（CN）6（phCH2NC5H5）3]·（H2O）4（Mr = 794.71） has been synthesized and its structure was characterized by IR, elemental analysis and X-my diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837（2）, b = 16.551（3）, c = 23.402（5） A, p = 97.531（4）°, V = 4161.0（15） A3, Z = 4, Dc = 1.269 g/cm^3, F（000） = 1668, p = 0.414 mm^-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three （phCH2N＋C5H5） ions, one [Fe（CN）6]^3- anion and four water molecules. According to the structural analysis, UFe（CN）6]^3- are linked together by O-H…N and O-H…O hydrogen bonds, but UFe（CN）6]^3- and [ （phCH2N＋ C5H5）3] ions are bound by electrostatic force to form an ionic compound.展开更多
A novel ionic compound [Fe（CN）6·（PhCHeNC9H7）4]·12H2O（C70H80FeN10O12, Mr = 1309.29） has been synthesized and its structure was characterized by I-R, elemental analysis and X-ray diffraction. The compoun...A novel ionic compound [Fe（CN）6·（PhCHeNC9H7）4]·12H2O（C70H80FeN10O12, Mr = 1309.29） has been synthesized and its structure was characterized by I-R, elemental analysis and X-ray diffraction. The compound crystaUizes in triclinic, space group P1, with a = 10.968（7）, b = 11.466（7）, c = 14.077（8）A, α= 87.014（7）, β= 78.124（7）, γ = 72.708（7）°, V = 1654.1（17）A3, Z = 1, Dc = 1.314 g·cm^-3, F（000） = 692, p = 0.298 mm^-1, the final R = 0.0519 and wR = 0.1355. The building unit of the title compound consists of four （PhCH2N＋C9H7） ions, one [Fe（CN）6]4- anion, and a dozen water molecules. According to the structural analysis, [Fe（CN）6]4- ions are linked together by O-H…O and O-H…N hydrogen bonds, while （PhCH2N＋C9HT） and [Fe（CN）6]4- ions interact with each other by electrostatic force to form an ionic compound.展开更多
Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terep...Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.展开更多
Molecular interactions of the ternary mixtures of 1-butyl-3-methylimidazolium chloride （[C4C1im]Cl）-water-2,6-dimethoxyphenol （2,6-DMP, a phenolic monomer lignin model compound） were investigated in comparison wit...Molecular interactions of the ternary mixtures of 1-butyl-3-methylimidazolium chloride （[C4C1im]Cl）-water-2,6-dimethoxyphenol （2,6-DMP, a phenolic monomer lignin model compound） were investigated in comparison with the [C4C1im]Cl-water binary systems through attenuated total reflection infrared spectroscopy. Results indicated that the microstructures of water and [C4C1im]Cl changed with varying mole fraction of [C4C1im]Cl （xIL） from 0.01 to 1.0. This change was mainly attributed to the interactions of [C4C1im]Cl-water and the self-aggregation of [C4C1im]Cl through hydrogen bonding. The band shifts of C-H on imidazolium ring and the functional groups in 2,6-DMP indicated that the occurrence of intermolecular interactions by different mechanisms （i.e., hydrogen bonding or π-π stacking） resulted in 2,6-DMP dissolution. In the case of xIL=0.12, the slightly hydrogen-bonded water was fully destroyed and [C4C1im]Cl existed in the form of hydrated ion pairs. Interestingly, the maximum 2,6-DMP solubility （238.5 g/100 g） was achieved in this case. The interactions and microstructures of [C4C1im]Cl-water mixtures influenced the dissolution behavior of 2,6-DMP.展开更多
A rapid and efficient, one pot synthesis of spirooxindole derivatives has been attempted by three- component reaction of isatin, malononitrile and carbonyl compound possessing a reactive c^-methylene group by using ta...A rapid and efficient, one pot synthesis of spirooxindole derivatives has been attempted by three- component reaction of isatin, malononitrile and carbonyl compound possessing a reactive c^-methylene group by using task specific ionic liquid, 1-butyl-3-methyl imidazolium hydroxide [bmim]OH as a catalyst. The important features of this methodology are straight forward route in short reaction time at room temperature and avoid any hazardous organic solvent, toxic catalyst, tedious purification step. Interestingly, this protocol is not only limited to mono-systems but also to the synthesis of newer bis- spirooxindole system. The separation of the product and reusability of the catalyst are easy with excellent yield. The [bmim]OH catalyst system could be reused up to five recycles without appreciable loss of activity.展开更多
A Csp3-Csp3 coupling production of the original ligand molecule [（CMeN（2,6-iPr2C6H3））2]2 （1） and an antimony ionic compound with α-diimine ligand [LH3]＋[SbCl4]-（2, L = [（2,6-iPrC6H3）NC（Me）]2） were synthe...A Csp3-Csp3 coupling production of the original ligand molecule [（CMeN（2,6-iPr2C6H3））2]2 （1） and an antimony ionic compound with α-diimine ligand [LH3]＋[SbCl4]-（2, L = [（2,6-iPrC6H3）NC（Me）]2） were synthesized and characterized by 1H NMR, elemental analysis and single-crystal X-ray structural analysis. The crystal of compound 1 belongs to the orthorhombic system, space group Pbca with a = 21.173（4）, b = 10.1639（17）, c = 22.954（4） , V = 4939.8（14） 3, C56H78N4, Mr = 807.22, Z = 4, Dc = 1.085 g/cm3, μ（MoKα） = 0.062 mm-1, F（000） = 1768, S = 0.998, the final R = 0.0593 and wR = 0.1616 for 6481 observed reflections （Ⅰ 〉 2σ（Ⅰ）） and R = 0.0819 and wR = 0.1805 for all 28753 data. The crystal of compound 2 belongs to the triclinic system, space group P with a = 10.930（2）, b = 12.553（2）, c = 12.561（3） , α = 89.780（7）, β = 82.861（6）, γ = 68.598（4）o, V = 1590.5（5） 3, C28H43Cl4N2Sb, Mr = 671.19, Z = 2, Dc = 1.401 g/cm3, μ（MoKα） = 1.222mm-1, F（000） = 688, S = 0.989, the final R = 0.0294 and wR = 0.0616 for 7578 observed reflections （Ⅰ 〉 2σ（Ⅰ）） and R = 0.0366 and wR = 0.0639 for all 16515 data. Complex 1 can be rationalized as a result of Csp3-Csp3 coupling of two ligand molecules. The reaction of corres- ponding potassium salts with Sb（Ⅲ） chloride resulted in the antimony complex 2, in which the cationic moiety [LH3]^＋ is balanced by the presence of [SbCl4]- anion.展开更多
基金supported by the National Key Research and Development Project from the Ministry of Science and Technology of China (No. 2021YFB3800103)National Natural Science Foundation of China (22209068)+1 种基金General Program of Basic Research in Shenzhen (JCYJ20220530112801004)the Major Program of Guangdong Basic and Applied Research Foundation (Nos. 2019B1515120083, 2019B121205001 and 2019B030302009)。
文摘Inorganic hole transport materials, particularly NiO_X, have shown considerable promise in boosting the efficiency and stability of perovskite solar cells. However, a major barrier to commercialization of NiO_X-based perovskite solar cells with positive-intrinsic-negative architectures is their direct contact with the absorbing layer, which can lead to losses of photovoltage and fill factor. Furthermore, highly positive under-coordinated Ni cations degrade the perovskite at the interface. Here, we address these issues with the use of an ionic compound(QAPyBF_(4)) as an additive to passivate defects throughout the perovskite layer and improve carrier conduction and interactions with under-coordinated Ni cations. Specifically,the highly electronegative inorganic anion [BF_(4)]~- interacts with the NiO_x/perovskite interface to passivate under-coordinated cations(Ni^(≥3+)). Accordingly, the decorated cells achieved a power conversion efficiency of 23.38% and a fill factor of 85.5% without a complex surface treatment or NiO_X doping.
基金financial support from the Natural Science Foundation of China(No.11904089,12174092,11674087)the Overseas Expertise Introduction Center for Discipline Innovation(D18025)+1 种基金the Program for Key Research and Development of Science and Technology in Hubei Province(grant No.2023BEB002)supported by the Young Science Foundation of Hubei University(Grant No.430/184303000047).
文摘Decoupling electrical and thermal properties to enhance the figure of merit of thermoelectric materials underscores an in-depth understanding of the mechanisms that govern the transfer of charge carriers.Typically,a factor that contributes to the optimization of thermal conductivity is often found to be detrimental to the electrical transport properties.Here,we systematically investigated 26 dimeric MX_(2)-type compounds(where M represents a metal and X represents a nonmetal element)to explore the influence of the electronic configurations of metal cations on lattice thermal transport and thermoelectric performance using first-principles calculations.A principled scheme has been identified that the filled outer orbitals of the cation lead to a significantly lower lattice thermal conductivity compared to that of the partly occupied case for MX_(2),due to the much weakened bonds manifested by the shallow potential well,smaller interatomic force constants,and higher atomic displacement parameters.Based on these findings,we propose two ionic compounds,BaAs and BaSe_(2),to realize reasonable high electrical conductivities through the structural anisotropy caused by the inserted covalent X_(2) dimers while still maintaining the large lattice anharmonicity.The combined superior electrical and thermal properties of BaSe_(2) lead to a high n-type thermoelectric ZT value of 2.3 at 500 K.This work clarifies the structural origin of the heat transport properties of dimeric MX_(2)-type compounds and provides an insightful strategy for developing promising thermoelectric materials.
基金Supported by the Doctoral Fund of Ministry of Education of China(20130181130006)the Key Program of National Natural Science Foundation of China(21336008)the National Natural Science Foundation of China(21476150)
文摘Switchable ionic compounds have wide applications in chemical processes.A switchable ionic compound based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU),CH_3OH and CO_2 was synthesized and characterized.DBU/CH_3OH/CO_2 ionic compound was prepared in the presence of excess methanol,and then the excess methanol was removed by reduced pressure distillation in CO_2 atmosphere.The product yield(100%) reached the theoretical maximum for the first time.Its structure was identified by NMR,FT-IR,and XRD.The crystal product shows 8strong peaks in XRD at 2θ values of 16.0547°,16.4308°,16.7651°,18.8714°,19.2140°,21.9471°,22.0780°,and25.5661°.Its decomposition onset temperature(53 ℃) was affirmed by TGA,which is lower than its melting point.And its ionic switch point was measured by conductivity.
基金funded by the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDA17040506)the National Key Research and Development Program of China (2017YFA0204800/2016YFA0202403)+6 种基金the Key Program project of the National Natural Science Foundation of China (51933010)the National Natural Science Foundation of China (61974085)the 111 Project (B21005)the Changjiang Scholars and Innovative Research Team (IRT_14R33)the National University Research Fund (GK201903051)the Research Start-up Fund from Shaanxi Normal University (1110020142)the Shanxi Science and Technology Department (20201101012).
文摘Interface engineering is an effective way to improve efficiency and long-term stability of perovskite solar cells(PSCs).Herein,an ionic compound tetrabutylammonium hexafluorophosphate(TP6)is adopted to passivate surface defects of the perovskite film.It is found that TP6 effectively reduced the surface defects,especially at the grain boundaries where the defects are abundant.Meanwhile,the exposed long alkyl chains and fluorine atoms in the TP6 enhanced the moisture stability of the perovskite film due to its strong hydrophobicity.In addition,the driving force of charge carrier separation and transport is increased by enlarged built-in potential.Consequently,the power conversion efficiency(PCE)of PSCs is significantly improved from 20.59% to 22.41%by increased open-circuit voltage(V_(oc))and fill factor(FF).The unencapsulated device with TP6 treatment exhibits better stability than the control device,and the PCE retains-80%of its initial PCE after 30 days under 15%-25%relative humidity in storage,while the PCE of the control device declines by more than 50%.
基金the Low Carbon Automation Manufacture Innovation Team 2011B81006 for the PhD studentshipNingbo Natural Science Foundation funding 2012A610094
文摘Room temperature ionic liquids(RTILs) are non-volatile organic salts. They may replace conventional coalescing agents in latex coating thus reducing volatile organic compounds(VOCs) emission as well as improving performance of latex coating products such as better thermal stability, conductivity, and antifouling property. The formation of latex coating containing RTILs can be achieved by encapsulation of RTILs inside particles via miniemulsion polymerization. In this study, the role of RTILs and its concentration on stability of miniemulsion during storage and polymerization were investigated. It has been found that, above a critical concentration(10 wt%), adding more RTILs to oil phase may weaken miniemulsion stability during storage as well as polymerization. Such observations were consistent with the zeta potential measurement for miniemulsions prepared at the similar conditions. The results obtained here would be a useful guideline for the development of new waterborne coating products with desirable functions and particle sizes.
文摘A novel ionic compound [Fe（CN）6（phCH2NC5H5）3]·（H2O）4（Mr = 794.71） has been synthesized and its structure was characterized by IR, elemental analysis and X-my diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837（2）, b = 16.551（3）, c = 23.402（5） A, p = 97.531（4）°, V = 4161.0（15） A3, Z = 4, Dc = 1.269 g/cm^3, F（000） = 1668, p = 0.414 mm^-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three （phCH2N＋C5H5） ions, one [Fe（CN）6]^3- anion and four water molecules. According to the structural analysis, UFe（CN）6]^3- are linked together by O-H…N and O-H…O hydrogen bonds, but UFe（CN）6]^3- and [ （phCH2N＋ C5H5）3] ions are bound by electrostatic force to form an ionic compound.
基金supported by the Natural Science Foundation of Education Committee of Henan Province (2006150016)
文摘A novel ionic compound [Fe（CN）6·（PhCHeNC9H7）4]·12H2O（C70H80FeN10O12, Mr = 1309.29） has been synthesized and its structure was characterized by I-R, elemental analysis and X-ray diffraction. The compound crystaUizes in triclinic, space group P1, with a = 10.968（7）, b = 11.466（7）, c = 14.077（8）A, α= 87.014（7）, β= 78.124（7）, γ = 72.708（7）°, V = 1654.1（17）A3, Z = 1, Dc = 1.314 g·cm^-3, F（000） = 692, p = 0.298 mm^-1, the final R = 0.0519 and wR = 0.1355. The building unit of the title compound consists of four （PhCH2N＋C9H7） ions, one [Fe（CN）6]4- anion, and a dozen water molecules. According to the structural analysis, [Fe（CN）6]4- ions are linked together by O-H…O and O-H…N hydrogen bonds, while （PhCH2N＋C9HT） and [Fe（CN）6]4- ions interact with each other by electrostatic force to form an ionic compound.
基金supported by the National Natural Science Foundation of China (Grant No.22278271)the Key Project of Education Department of Liaoning Province(Grant No.LZGD2020005)
文摘Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.
基金This work was supported by the National Natural Science Foundation of China （No.21106011 and No.21276034） and the Program of Science and Technology of Liaoning Province （No.201602058）, and China Scholarship Council.
文摘Molecular interactions of the ternary mixtures of 1-butyl-3-methylimidazolium chloride （[C4C1im]Cl）-water-2,6-dimethoxyphenol （2,6-DMP, a phenolic monomer lignin model compound） were investigated in comparison with the [C4C1im]Cl-water binary systems through attenuated total reflection infrared spectroscopy. Results indicated that the microstructures of water and [C4C1im]Cl changed with varying mole fraction of [C4C1im]Cl （xIL） from 0.01 to 1.0. This change was mainly attributed to the interactions of [C4C1im]Cl-water and the self-aggregation of [C4C1im]Cl through hydrogen bonding. The band shifts of C-H on imidazolium ring and the functional groups in 2,6-DMP indicated that the occurrence of intermolecular interactions by different mechanisms （i.e., hydrogen bonding or π-π stacking） resulted in 2,6-DMP dissolution. In the case of xIL=0.12, the slightly hydrogen-bonded water was fully destroyed and [C4C1im]Cl existed in the form of hydrated ion pairs. Interestingly, the maximum 2,6-DMP solubility （238.5 g/100 g） was achieved in this case. The interactions and microstructures of [C4C1im]Cl-water mixtures influenced the dissolution behavior of 2,6-DMP.
文摘A rapid and efficient, one pot synthesis of spirooxindole derivatives has been attempted by three- component reaction of isatin, malononitrile and carbonyl compound possessing a reactive c^-methylene group by using task specific ionic liquid, 1-butyl-3-methyl imidazolium hydroxide [bmim]OH as a catalyst. The important features of this methodology are straight forward route in short reaction time at room temperature and avoid any hazardous organic solvent, toxic catalyst, tedious purification step. Interestingly, this protocol is not only limited to mono-systems but also to the synthesis of newer bis- spirooxindole system. The separation of the product and reusability of the catalyst are easy with excellent yield. The [bmim]OH catalyst system could be reused up to five recycles without appreciable loss of activity.
基金supported by the National Natural Science Foundation of China (No. 21001016 and 20902112)
文摘A Csp3-Csp3 coupling production of the original ligand molecule [（CMeN（2,6-iPr2C6H3））2]2 （1） and an antimony ionic compound with α-diimine ligand [LH3]＋[SbCl4]-（2, L = [（2,6-iPrC6H3）NC（Me）]2） were synthesized and characterized by 1H NMR, elemental analysis and single-crystal X-ray structural analysis. The crystal of compound 1 belongs to the orthorhombic system, space group Pbca with a = 21.173（4）, b = 10.1639（17）, c = 22.954（4） , V = 4939.8（14） 3, C56H78N4, Mr = 807.22, Z = 4, Dc = 1.085 g/cm3, μ（MoKα） = 0.062 mm-1, F（000） = 1768, S = 0.998, the final R = 0.0593 and wR = 0.1616 for 6481 observed reflections （Ⅰ 〉 2σ（Ⅰ）） and R = 0.0819 and wR = 0.1805 for all 28753 data. The crystal of compound 2 belongs to the triclinic system, space group P with a = 10.930（2）, b = 12.553（2）, c = 12.561（3） , α = 89.780（7）, β = 82.861（6）, γ = 68.598（4）o, V = 1590.5（5） 3, C28H43Cl4N2Sb, Mr = 671.19, Z = 2, Dc = 1.401 g/cm3, μ（MoKα） = 1.222mm-1, F（000） = 688, S = 0.989, the final R = 0.0294 and wR = 0.0616 for 7578 observed reflections （Ⅰ 〉 2σ（Ⅰ）） and R = 0.0366 and wR = 0.0639 for all 16515 data. Complex 1 can be rationalized as a result of Csp3-Csp3 coupling of two ligand molecules. The reaction of corres- ponding potassium salts with Sb（Ⅲ） chloride resulted in the antimony complex 2, in which the cationic moiety [LH3]^＋ is balanced by the presence of [SbCl4]- anion.
