A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- po...A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- polyanions within the intercrystalline voids as pillars and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 11.430（3）, b = 12.242（3）, c = 14.279（3）A, α = 106.196（4）,β = 94.316（4）, γ = 98.294（3）°, V = 1884.5（7）A^3 Z = 1, C44H50N10O54CoEMo12Si, Mr = 2880.17, Dc = 2.538 g/cm^3, p = 2.484 mm^-1,F（000） = 1388, the final R = 0.0383 and wR = 0.1096 for 7753 observed reflections with I 〉 2σ（I）. Flack factor is 0.22（3）. Compound 1 is a pillar-layered framework with the [SiMo12O40]^4- anions linearly located on the square voids between the 2D bilayers which are formed by the dpdo ligands and cobalt（II） ions.展开更多
Materials capable of tunable optical absorption and fluorescence properties in response to multiple external stimuli,while providing a readable signal,have garnered significant scientific interest.Such materials hold ...Materials capable of tunable optical absorption and fluorescence properties in response to multiple external stimuli,while providing a readable signal,have garnered significant scientific interest.Such materials hold promise for applications in wearable electronics,anticounterfeiting technologies,self-powered light sources and displays,human-machine interfaces,and intelligent sensing systems.A highly effective approach to achieving multi-stimuli optical responsiveness is to integrate various functionalities into a single structure,such as reversible electrochemistry,ion and electronic charge transport,photoluminescence,and supramolecular organization(e.g.,mesomorphism).Here,we introduce a new class of thermotropic smectic ionic liquid crystals,composed of the bistriflimide salts ofπ-conjugated fluorenoviologen dications.The dications feature a central fluorene core functionalized in position 2,7 with two pyridine moieties,whose nitrogen atoms are alkylated with promesogenic alkyl chains of varying lengths.In their bulk liquid crystalline phases,these materials exhibit ON/OFF electrofluorochromism(under UV photoexcitation),with voltage-triggered fluorescence quenching and a shift from yellow to dark electrochromism.Additionally,they display thermofluorochromism,showing a striking fluorescence color change from green to blue on going from the crystalline solid phase at room temperature to the liquid crystalline phases at high temperatures.展开更多
Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, ...Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.展开更多
A novel connectivity index ^mG based on adjacency matrix of molecular graphs was proposed as follows： ^mG = ∑（gi·gj·g…）^0.5. The element gi of adjacency matrix was defined as gi=（1＋Zi^1.4）/（1＋ri^1....A novel connectivity index ^mG based on adjacency matrix of molecular graphs was proposed as follows： ^mG = ∑（gi·gj·g…）^0.5. The element gi of adjacency matrix was defined as gi=（1＋Zi^1.4）/（1＋ri^1.4）, where Zi and ri are the charge number and the thermochemical radius of ion i respectively, and the radii ri for metal ions are taken to be the Goldschmidt radius. The regression analysis by the connectivity index 1G can provide a high-quality QSPR model for the lattice energies of 245 complex inorganic ionic crystal samples. The results imply, that the lattice energies may be expressed as a linear model of the connectivity index 1G. For the linear model the correlation coefficient r and the standard error s are 0.9998 and 228.72 kJ/mol, respectively. The cross-validation by the leave-one-out method demonstrates that the model is highly reliable from the point of view of statistics.展开更多
Polyoxometalates(POMs)with multiple redox active sites have been reported as charge sponge for lithium-ion batteries(LIBs).Herein,we for the first time introduce a polyoxovanadate(POV)ionic crystals with macrocations,...Polyoxometalates(POMs)with multiple redox active sites have been reported as charge sponge for lithium-ion batteries(LIBs).Herein,we for the first time introduce a polyoxovanadate(POV)ionic crystals with macrocations,[Ni(Phen)_(3)][ClV_(14)O_(34)]Cl(NiV_(14),Phen=1,10-phenanthroline),as an anode material for LIBs.The existence of macrocation[Ni(Phen)_(3)]^(2+)stabilizes the open tunnels inside NiV_(14).The NiV_(14)electrode exhibits superior rate capabilities(1083 mAh·g^(-1)at 100 mA·g^(-1)and 384 mAh·g^(-1)at 2000 mA·g^(-1))due to the rapid capacitive dominated contribution and high Li^(+)ions diffusion coefficients(3.3×10^(-12) cm^(-2)·s^(-1)),and it delivers a remarkable cycling stability with a Coulombic efficiency of 99.7%after 1000 cycles at 2000 mA·g^(-1).Such performance can be attributed to the stable structure of NiV14 and the highly reversible valence changes of vanadium during the charge/discharge processes,which are revealed by a combination of in situ X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),and X-ray absorption fine structure(XAFS)measurements.This work not only demonstrates that NiV_(14) with open tunnels stabilized by macrocation is a promising anode material for high performance LIBs,but also provides important references for the rational design of POMs electrode materials in advanced energy storage systems.展开更多
A theory of ultrasonic generation via direct interaction of transverse optic (TO) phonons with photons in anharmonic lattice of ionic crystals is presented. There are two methods of supplying light energy for the exci...A theory of ultrasonic generation via direct interaction of transverse optic (TO) phonons with photons in anharmonic lattice of ionic crystals is presented. There are two methods of supplying light energy for the excitation of TO lattice wave as a high frequency ultrasound: (A) incident light comes from the source outside the cavity? fulfilled with ionic crystal medium, (B) photon mode of the cavity possesses the gain of amplification by stimulated radiation of active atoms doping in the medium. More attention is drawn to the case (B). The working system of case (B), as a mixture of lasing action and ultrasonic generation, has the threshold phenomena like usual laser. And the linear stability analysis shows that the nonlineax phonon-photon coupling and the interaction among phonons themselves, both of which reflect the anharmonicity of lattice vibration, are necessary to the stable ultrasonic output. So this laser-ultrasonic generation mixture would be also a measure to investigate the lattice-dynamic nonlinearity and correlated electromagnetic properties of ionic crystals.展开更多
Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctylox...Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctyloxybenzoic acid,and 3,4,5- trioctyloxybenzoic acid）.The solid structure and properties were monitored with FT-IR,XRD,TG,DSC,and polarized optical microscope（POM）.Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures： lamella for the mono-,disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes.These corresponded to the ionic thermotropic liquid crystal SmA andΦ_h phases,respectively.This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.展开更多
Liquid plasticizers with a relatively higher dielectric coefficient like ethylene carbonate(EC),propylene carbonate(PC),and ethyl methyl carbonate(EMC) are the most commonly used electrolyte materials in commercial re...Liquid plasticizers with a relatively higher dielectric coefficient like ethylene carbonate(EC),propylene carbonate(PC),and ethyl methyl carbonate(EMC) are the most commonly used electrolyte materials in commercial rechargeable lithium batteries(LIBs) due to their outstanding dissociation ability to lithium salts.However,volatility and fluidity result in their inevitable demerits like leakage and potential safety problem of the final LIBs.Here we for the first time device a subtle method to prepare a novel thermal-stable and non-fluid poly(carbonate) solid-state electrolyte to merge EC with lithium carriers.To this aim,a series of carbonate substituted imidazole ionic plastic crystals(G-NTOC) with different polymerization degrees have been synthesized.The resulting G-NTOC shows an excellent solid-state temperature window(R.T.-115℃).More importantly,the maximum ionic conductivity and lithium transference number of the prepared G-NTOC reach 0.36 × 10^(-3) S cm^(-1) and 0.523 at 30℃,respectively.Galvanostatic cycling test results reveal that the developed G-NTOC solid-state electrolytes are favorable to restraining the growth of lithium dendrite due to the excellent compatibility between the electrode and the produced plastic crystal electrolyte.The fabricated LiIG-NTOCILiFeP04 all-solid-state cell initially delivers a maximum discharge capacity of 152.1 mAh g^(-1) at the discharge rate of 0.1 C.After chargingdischarging the cell for 60 times,Coulombic efficiency of the solid-state cell still exceeds 97%.Notably,the LiIG-NTOCILiFeP04 cell can stably light a commercial LED with a rated power of 0.06 W for more than1 h at 30℃,and the output power nearly maintains unchanged with the charging-discharging cycling test,implying a sizeable potential application in the next generation of solid-state LIBs.展开更多
Organic ionic plastic crystals (OIPCs) composed of 1-ethyl-1-methyl pyrrolidinium bis(fluorosulfonyl) imide (P12FSI) and lithium bis(fluorosulfonyl)imide (LiFSI) was used as electrolyte for lithium-oxygen batteries. S...Organic ionic plastic crystals (OIPCs) composed of 1-ethyl-1-methyl pyrrolidinium bis(fluorosulfonyl) imide (P12FSI) and lithium bis(fluorosulfonyl)imide (LiFSI) was used as electrolyte for lithium-oxygen batteries. Since P12FSI-LiFSI electrolyte exhibited high ionic conductivity, good chemical stability and wide electrochemical window, the battery showed good rate capability, excellent cycling stability and can be operated stably for 320 cycles under a fixed capacity of 500 mAh/gcarbon. The use of OIPCs electrolyte could provide a new avenue for the development of high-performance Li-O2 batteries.展开更多
Ionic liquid 1-hexadecyl-3-methylimidazolium bromide [C16mim]Br was synthesized by solvent-free alkylation of N-methylimidzole with hexadecyl bromide. A large transparent single crystal of 1-hexadecyl-3-methylimidazol...Ionic liquid 1-hexadecyl-3-methylimidazolium bromide [C16mim]Br was synthesized by solvent-free alkylation of N-methylimidzole with hexadecyl bromide. A large transparent single crystal of 1-hexadecyl-3-methylimidazolium bromide monohydrate （[C16mim]Br·H2O）, 4 mm in length, was firstly obtained in the water-trichloromethane-toluene growth system （Vwater＇Vtrichloromethane＇Vtoluene = 0.1：1：2）. The crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in the triclinic system, space group P1, with a = 5.4962（15）, b = 7.839（2）, c = 27.279（8） A, α = 94.375, β = 91.500, γ = 101.999°, Z = 2, V = 1145.2（5） A3, C20H41BrN2O, Mr = 405.46, Dc = 1.176 Mg/m3, μ = 1.804 mm^-1, F（000） = 436, the final R = 0.0523 and wR = 0.1345. The 3D supramolecular structure is constructed through weak interactions between imidazolium cations, Br- anions and lattice water molecules. The long alkyl chain to the imidazolium ring and lattice water molecules play an important role in the self-assembly process. Moreover, it is proposed that [C16mim]Br in water has aggregation behavior and the possible self-assembled structure is the interdigitated pattern. Finally, thermal stability of [C16mim][Br]·H2O was also studied by DSC and TGA analysis.展开更多
Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of dif...Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.展开更多
To investigate the performance of graphene(Gra) modified with ethoxycarbonyl ionic liquid(IL), chain mobility and crystallization kinetics of poly(L-lactic acid)(PLLA), a series of PLLA nanocomposites have been prepar...To investigate the performance of graphene(Gra) modified with ethoxycarbonyl ionic liquid(IL), chain mobility and crystallization kinetics of poly(L-lactic acid)(PLLA), a series of PLLA nanocomposites have been prepared using solution-cast method.IL can improve the dispersion of Gra in PLLA matrix and the samples containing IL have higher growth rate of PLLA spherulite than neat PLLA does. PLLA/IL/Gra and PLLA/2 Gra exhibit the same relaxation strength and time of αN relaxation that corresponds to the longest normal mode motion at 110-140 °C. PLLA/IL/Gra shows a faster crystallization rate than PLLA/2 Gra does, which might be attributed to the Gra-imidazolium cation interaction in IL modified Gra, the significant dispersion effect of IL at Gra surface, and the increase of nuclei density of PLLA/IL/Gra.展开更多
Redox-active polyelectrolyte-surfactant complexes（PSC） were prepared via the ionic self-assembly of sodium poly（styrenesulfonate） （PSS） and ferrocenyl surfactant,（11-ferrocenylundecyl）trimethylammonium bromide...Redox-active polyelectrolyte-surfactant complexes（PSC） were prepared via the ionic self-assembly of sodium poly（styrenesulfonate） （PSS） and ferrocenyl surfactant,（11-ferrocenylundecyl）trimethylammonium bromide（FTMA） in aqueous solution. The PSS-FTMA complex exhibited an ordered interdigitated monolayer mesomorphous structure with the long period of d = 3.13 nm,and was in the ionic thermotropic liquid crystal SmA state at room temperature.Interestingly,in the solid complex, the ferrocenyl moieties formed H-aggregation showing an increase in theπ-π~＊ energy transfer of cyclopentadienes in the ferrocene moieties as known from the blue-shift in the UV spectrum.The complexes showed higher thermal stability compared with their components due to the ionic interaction.The PSS-FTMA film had a good redox reversibility,which promised to be used in electrochemical sensors.展开更多
In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The ...In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The results showed that the control ability of ionic liquids for CaCO3 crystals growth was dependent on the counter anion very much.展开更多
A polycaprolactone-graffed cellulose nanocrystal （PCL-g-CN） was prepared in ionic liquid and characterized by Fourier transform infrared spectrum （FT-IR）, X-ray diffraction （XRD）, and transmission electron micro...A polycaprolactone-graffed cellulose nanocrystal （PCL-g-CN） was prepared in ionic liquid and characterized by Fourier transform infrared spectrum （FT-IR）, X-ray diffraction （XRD）, and transmission electron microscopy （TEM）. A peak assigned to the carbonyl group appears at 1 730 cm-1 in the FT-IR of PCL-g-CN, which confirms that the grafting reaction is suc- cessfully completed. The morphologies of PCL-g-CNs still main- tain rod-like structure according to the TEM images. XRD results show that the crystal type of the PCL-g-CNs changed from cellu- lose I to cellulose II. The reasons for crystal transition of CNs turn out to be combined effects of anion and cation in ionic liquid with CNs.展开更多
Herein a novel aminopropyl-containing ionic liquid based organosilica(ILOS-NH_2) is prepared, characterized and applied as effective adsorbent for removal of crystal violet(CV) dye from wastewater. The ILOS-NH2 materi...Herein a novel aminopropyl-containing ionic liquid based organosilica(ILOS-NH_2) is prepared, characterized and applied as effective adsorbent for removal of crystal violet(CV) dye from wastewater. The ILOS-NH2 material was synthesized by hydrolysis and co-condensation of 1,3-bis-(3-trimethoxysilylpropyl)-imidazolium chloride(BTMSPIC) under acidic conditions followed by treatment with 3-aminopropyl-trimethoxysilane in toluene under reflux conditions. This material was characterized using scanning electron microscopy(SEM), diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS), thermal gravimetric analysis(TGA) and energy dispersive X-ray analysis(EDAX). The material was effectively used in the removal of crystal violet at ambient temperature and showed high capacity and stability under applied conditions. The efficacy of p H, contact time, adsorbent dose, initial dye concentration, temperature, and isotherm studies and the applicability of pseudo-first, second order and Elovich kinetic models have also been investigated.展开更多
Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such ...Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such as high ionic conductivity,non-flammability,and plasticity.Various nuclear magnetic resonance(NMR)spectroscopy techniques including solid-state NMR,pulsed-field gradient(PFG)NMR,and magnetic resonance imaging(MRI)etc.,provide us a versatile toolkit to understand the fundamental level structures,molecular dynamics,and ionic interactions in these materials.This article reviews the commonly used NMR methods including solid-and solution-state NMR,PFG-NMR,dynamic nuclear polarization(DNP)and the application of these methods in revealing the microscopic level structures and ion-transport mechanisms in OIPC materials.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
The title compound, [Nd(dmso) 7Cl][Bph 4] 2(dmso=dimethylsulfoxide, Bph 4=tetraphenylboron anion) was synthesized in organic solvent acetone/EtOH and the structure was determined by single crystal X ray diffract...The title compound, [Nd(dmso) 7Cl][Bph 4] 2(dmso=dimethylsulfoxide, Bph 4=tetraphenylboron anion) was synthesized in organic solvent acetone/EtOH and the structure was determined by single crystal X ray diffraction. The crystal is triclinic with space group P 1, and the crystal data are as follows: a =1 2554(1) nm, b = 1 2799(1) nm, c =2 4598(3) nm; α =93 53(1)°, β =104 50(1)°, γ =112 77(1)°, V =3 4722(6) nm 3, Z =2, M r=1365 01, D c=1 306 g·cm -3 . The crystal is composed of a big cation [Nd(dmso) 7Cl] 2+ and two big anions [BPh 4] -. The Nd 3+ is coordinated by a chlorine atom and seven oxygen atoms from seven dimethylsulfoxides forming a distorted square antiprism coordination polyhedron,while the BPh - 4 anion is charge equilibrium ion.展开更多
For a long time,researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates(POMs).Modifying POMs with various types and properties of metals has broadened thei...For a long time,researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates(POMs).Modifying POMs with various types and properties of metals has broadened their applications in fields such as magnetism,luminescence,and catalysis.However,despite the discovery of numerous POM structures doped with transition metal ions,the development of aluminum(Al)as aⅢA group metal in the POM field has been slow.Aluminum,the most abundant metal in nature,offers innate electron-deficient properties that,when combined with highly charged POMs,could introduce novel structures and excellent functionalities like proton conduction to this field.Therefore,this review will address the gap in summarizing Al-containing POMs by categorizing and summarizing the synthesis,structural characteristics,and properties of Al-containing POMs,aiming to provide a theoretical foundation for exploring POM structures doped with Al atoms.The review also analyzes and forecasts the prospects in this field.展开更多
基金supported by the Natural Science Foundation of Henan Province
文摘A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- polyanions within the intercrystalline voids as pillars and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 11.430（3）, b = 12.242（3）, c = 14.279（3）A, α = 106.196（4）,β = 94.316（4）, γ = 98.294（3）°, V = 1884.5（7）A^3 Z = 1, C44H50N10O54CoEMo12Si, Mr = 2880.17, Dc = 2.538 g/cm^3, p = 2.484 mm^-1,F（000） = 1388, the final R = 0.0383 and wR = 0.1096 for 7753 observed reflections with I 〉 2σ（I）. Flack factor is 0.22（3）. Compound 1 is a pillar-layered framework with the [SiMo12O40]^4- anions linearly located on the square voids between the 2D bilayers which are formed by the dpdo ligands and cobalt（II） ions.
基金the Ministero dell'Universita e della Ricerca Italiano(MUR)and the University of Calabria for supporting this project in the framework of the ex 60%budget grant.G.A.C.and A.B.acknowledge the financial support from MUR postdoctoral fellowship DM 737/2021-Grant b.(CUP H25F21001420001).
文摘Materials capable of tunable optical absorption and fluorescence properties in response to multiple external stimuli,while providing a readable signal,have garnered significant scientific interest.Such materials hold promise for applications in wearable electronics,anticounterfeiting technologies,self-powered light sources and displays,human-machine interfaces,and intelligent sensing systems.A highly effective approach to achieving multi-stimuli optical responsiveness is to integrate various functionalities into a single structure,such as reversible electrochemistry,ion and electronic charge transport,photoluminescence,and supramolecular organization(e.g.,mesomorphism).Here,we introduce a new class of thermotropic smectic ionic liquid crystals,composed of the bistriflimide salts ofπ-conjugated fluorenoviologen dications.The dications feature a central fluorene core functionalized in position 2,7 with two pyridine moieties,whose nitrogen atoms are alkylated with promesogenic alkyl chains of varying lengths.In their bulk liquid crystalline phases,these materials exhibit ON/OFF electrofluorochromism(under UV photoexcitation),with voltage-triggered fluorescence quenching and a shift from yellow to dark electrochromism.Additionally,they display thermofluorochromism,showing a striking fluorescence color change from green to blue on going from the crystalline solid phase at room temperature to the liquid crystalline phases at high temperatures.
文摘Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.
基金Project supported by the University Natural Science Foundation of Jiangsu Province （No. 04KJD150195）.Acknowledgement The authors wish to express our gratitude to the referees for their valuable comments.
文摘A novel connectivity index ^mG based on adjacency matrix of molecular graphs was proposed as follows： ^mG = ∑（gi·gj·g…）^0.5. The element gi of adjacency matrix was defined as gi=（1＋Zi^1.4）/（1＋ri^1.4）, where Zi and ri are the charge number and the thermochemical radius of ion i respectively, and the radii ri for metal ions are taken to be the Goldschmidt radius. The regression analysis by the connectivity index 1G can provide a high-quality QSPR model for the lattice energies of 245 complex inorganic ionic crystal samples. The results imply, that the lattice energies may be expressed as a linear model of the connectivity index 1G. For the linear model the correlation coefficient r and the standard error s are 0.9998 and 228.72 kJ/mol, respectively. The cross-validation by the leave-one-out method demonstrates that the model is highly reliable from the point of view of statistics.
基金We acknowledge support from Hefei National Laboratory for Physical Sciences at the Microscale,Hefei Science Center of Chinese Academy of Sciences,Fujian Institute of Innovation of Chinese Academy of Sciences,the National Natural Science Foundation of China(Nos.21571167,51502282,and 22075266)the Fundamental Research Funds for the Central Universities(Nos.WK2060190053 and WK2060190100).
文摘Polyoxometalates(POMs)with multiple redox active sites have been reported as charge sponge for lithium-ion batteries(LIBs).Herein,we for the first time introduce a polyoxovanadate(POV)ionic crystals with macrocations,[Ni(Phen)_(3)][ClV_(14)O_(34)]Cl(NiV_(14),Phen=1,10-phenanthroline),as an anode material for LIBs.The existence of macrocation[Ni(Phen)_(3)]^(2+)stabilizes the open tunnels inside NiV_(14).The NiV_(14)electrode exhibits superior rate capabilities(1083 mAh·g^(-1)at 100 mA·g^(-1)and 384 mAh·g^(-1)at 2000 mA·g^(-1))due to the rapid capacitive dominated contribution and high Li^(+)ions diffusion coefficients(3.3×10^(-12) cm^(-2)·s^(-1)),and it delivers a remarkable cycling stability with a Coulombic efficiency of 99.7%after 1000 cycles at 2000 mA·g^(-1).Such performance can be attributed to the stable structure of NiV14 and the highly reversible valence changes of vanadium during the charge/discharge processes,which are revealed by a combination of in situ X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),and X-ray absorption fine structure(XAFS)measurements.This work not only demonstrates that NiV_(14) with open tunnels stabilized by macrocation is a promising anode material for high performance LIBs,but also provides important references for the rational design of POMs electrode materials in advanced energy storage systems.
基金This work is supported by the National Nature Science Foundation of China!(No. 69678003)
文摘A theory of ultrasonic generation via direct interaction of transverse optic (TO) phonons with photons in anharmonic lattice of ionic crystals is presented. There are two methods of supplying light energy for the excitation of TO lattice wave as a high frequency ultrasound: (A) incident light comes from the source outside the cavity? fulfilled with ionic crystal medium, (B) photon mode of the cavity possesses the gain of amplification by stimulated radiation of active atoms doping in the medium. More attention is drawn to the case (B). The working system of case (B), as a mixture of lasing action and ultrasonic generation, has the threshold phenomena like usual laser. And the linear stability analysis shows that the nonlineax phonon-photon coupling and the interaction among phonons themselves, both of which reflect the anharmonicity of lattice vibration, are necessary to the stable ultrasonic output. So this laser-ultrasonic generation mixture would be also a measure to investigate the lattice-dynamic nonlinearity and correlated electromagnetic properties of ionic crystals.
基金the financial support from the NSFC(No50873037)the PCSIRT(NoIRT0827)+2 种基金the Fundamental Research Funds for the Central Universities(No2009ZM0017)China Postdoctoral Science Foundation(No20100470908)the NSF of Guangdong Province(No10451064101005118) is gratefully acknowledged
文摘Three polymer-amphiphile complexes were prepared by combining poly（allylamine hydrochloride）（PAH） with the potassium salt of mono-,di-,and trisubstituted benzoic acid dendrons（4-octyloxybenzoic acid,3,5-dioctyloxybenzoic acid,and 3,4,5- trioctyloxybenzoic acid）.The solid structure and properties were monitored with FT-IR,XRD,TG,DSC,and polarized optical microscope（POM）.Difference in the tail chain number of the dendritic amphiphile induced two different mesomorphous structures： lamella for the mono-,disubstituted dendron containing complexes and hexagonal column for the trisubstituted dendron containing complexes.These corresponded to the ionic thermotropic liquid crystal SmA andΦ_h phases,respectively.This finding is significant for design of functional nanostructures based on the ionic complexation of polymers and amphiphiles.
基金the financial support of the National Natural Science Foundation of China (21961044, 22169024)the Yunnan University’s Research Innovation Fund for graduate students (2021Y394)。
文摘Liquid plasticizers with a relatively higher dielectric coefficient like ethylene carbonate(EC),propylene carbonate(PC),and ethyl methyl carbonate(EMC) are the most commonly used electrolyte materials in commercial rechargeable lithium batteries(LIBs) due to their outstanding dissociation ability to lithium salts.However,volatility and fluidity result in their inevitable demerits like leakage and potential safety problem of the final LIBs.Here we for the first time device a subtle method to prepare a novel thermal-stable and non-fluid poly(carbonate) solid-state electrolyte to merge EC with lithium carriers.To this aim,a series of carbonate substituted imidazole ionic plastic crystals(G-NTOC) with different polymerization degrees have been synthesized.The resulting G-NTOC shows an excellent solid-state temperature window(R.T.-115℃).More importantly,the maximum ionic conductivity and lithium transference number of the prepared G-NTOC reach 0.36 × 10^(-3) S cm^(-1) and 0.523 at 30℃,respectively.Galvanostatic cycling test results reveal that the developed G-NTOC solid-state electrolytes are favorable to restraining the growth of lithium dendrite due to the excellent compatibility between the electrode and the produced plastic crystal electrolyte.The fabricated LiIG-NTOCILiFeP04 all-solid-state cell initially delivers a maximum discharge capacity of 152.1 mAh g^(-1) at the discharge rate of 0.1 C.After chargingdischarging the cell for 60 times,Coulombic efficiency of the solid-state cell still exceeds 97%.Notably,the LiIG-NTOCILiFeP04 cell can stably light a commercial LED with a rated power of 0.06 W for more than1 h at 30℃,and the output power nearly maintains unchanged with the charging-discharging cycling test,implying a sizeable potential application in the next generation of solid-state LIBs.
基金supported by the National Key R&D Program of China (No.2016YFB0901505)National Natural Science Foundation of China(No. 21573145)
文摘Organic ionic plastic crystals (OIPCs) composed of 1-ethyl-1-methyl pyrrolidinium bis(fluorosulfonyl) imide (P12FSI) and lithium bis(fluorosulfonyl)imide (LiFSI) was used as electrolyte for lithium-oxygen batteries. Since P12FSI-LiFSI electrolyte exhibited high ionic conductivity, good chemical stability and wide electrochemical window, the battery showed good rate capability, excellent cycling stability and can be operated stably for 320 cycles under a fixed capacity of 500 mAh/gcarbon. The use of OIPCs electrolyte could provide a new avenue for the development of high-performance Li-O2 batteries.
基金Supported by the Natural Science Basic Research Plan in Shaanxi Province (No.2007K071)
文摘Ionic liquid 1-hexadecyl-3-methylimidazolium bromide [C16mim]Br was synthesized by solvent-free alkylation of N-methylimidzole with hexadecyl bromide. A large transparent single crystal of 1-hexadecyl-3-methylimidazolium bromide monohydrate （[C16mim]Br·H2O）, 4 mm in length, was firstly obtained in the water-trichloromethane-toluene growth system （Vwater＇Vtrichloromethane＇Vtoluene = 0.1：1：2）. The crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in the triclinic system, space group P1, with a = 5.4962（15）, b = 7.839（2）, c = 27.279（8） A, α = 94.375, β = 91.500, γ = 101.999°, Z = 2, V = 1145.2（5） A3, C20H41BrN2O, Mr = 405.46, Dc = 1.176 Mg/m3, μ = 1.804 mm^-1, F（000） = 436, the final R = 0.0523 and wR = 0.1345. The 3D supramolecular structure is constructed through weak interactions between imidazolium cations, Br- anions and lattice water molecules. The long alkyl chain to the imidazolium ring and lattice water molecules play an important role in the self-assembly process. Moreover, it is proposed that [C16mim]Br in water has aggregation behavior and the possible self-assembled structure is the interdigitated pattern. Finally, thermal stability of [C16mim][Br]·H2O was also studied by DSC and TGA analysis.
文摘Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [R_ n NH_ 4- n ][PhSn( μ 2-SCH_2COO)_2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [( i -Pr)_2NH_2] [PhSn( μ 2-SCH_2COO)_2] was determined by X-ray diffraction. In the crystal structure,the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a =1.1766(11) nm, b =1.3144(14) nm, c =1.3336(15) nm,β =90° and Z =4.
基金financially supported by the National Natural Science Foundation of China(No.51603060)the Fundamental Research Funds for the Central Universities(No.JZ2017YYPY0250)
文摘To investigate the performance of graphene(Gra) modified with ethoxycarbonyl ionic liquid(IL), chain mobility and crystallization kinetics of poly(L-lactic acid)(PLLA), a series of PLLA nanocomposites have been prepared using solution-cast method.IL can improve the dispersion of Gra in PLLA matrix and the samples containing IL have higher growth rate of PLLA spherulite than neat PLLA does. PLLA/IL/Gra and PLLA/2 Gra exhibit the same relaxation strength and time of αN relaxation that corresponds to the longest normal mode motion at 110-140 °C. PLLA/IL/Gra shows a faster crystallization rate than PLLA/2 Gra does, which might be attributed to the Gra-imidazolium cation interaction in IL modified Gra, the significant dispersion effect of IL at Gra surface, and the increase of nuclei density of PLLA/IL/Gra.
基金The financial support from the NSFC(No50873037)China Postdoctoral Science Foundation(Nos20100470908 and 201104349)the NSF of Guangdong Province(No10451064101005118)
文摘Redox-active polyelectrolyte-surfactant complexes（PSC） were prepared via the ionic self-assembly of sodium poly（styrenesulfonate） （PSS） and ferrocenyl surfactant,（11-ferrocenylundecyl）trimethylammonium bromide（FTMA） in aqueous solution. The PSS-FTMA complex exhibited an ordered interdigitated monolayer mesomorphous structure with the long period of d = 3.13 nm,and was in the ionic thermotropic liquid crystal SmA state at room temperature.Interestingly,in the solid complex, the ferrocenyl moieties formed H-aggregation showing an increase in theπ-π~＊ energy transfer of cyclopentadienes in the ferrocene moieties as known from the blue-shift in the UV spectrum.The complexes showed higher thermal stability compared with their components due to the ionic interaction.The PSS-FTMA film had a good redox reversibility,which promised to be used in electrochemical sensors.
文摘In this paper, the effect of ionic liquids on the CaCO3 crystal growth has been studied for the first time. The obtained CaCO3 crystals were charactered by the X-ray diffraction and scanning electron micrographs. The results showed that the control ability of ionic liquids for CaCO3 crystals growth was dependent on the counter anion very much.
基金Supported by Supporting Project of New Century Excellent Talents of Ministry of Education of China(NCET-11-0686)Fundamental Research Funds for the Central Universities(Self-Determined and Innovative Research Funds of WUT 2012-Ia-006)+1 种基金ecoENERGY Innovation Initiative of Canada,Program of Energy Research and Development(PERD)of CanadaState Key Laboratory of Pulp and Paper Engineering,South China University of Technology(201212)
文摘A polycaprolactone-graffed cellulose nanocrystal （PCL-g-CN） was prepared in ionic liquid and characterized by Fourier transform infrared spectrum （FT-IR）, X-ray diffraction （XRD）, and transmission electron microscopy （TEM）. A peak assigned to the carbonyl group appears at 1 730 cm-1 in the FT-IR of PCL-g-CN, which confirms that the grafting reaction is suc- cessfully completed. The morphologies of PCL-g-CNs still main- tain rod-like structure according to the TEM images. XRD results show that the crystal type of the PCL-g-CNs changed from cellu- lose I to cellulose II. The reasons for crystal transition of CNs turn out to be combined effects of anion and cation in ionic liquid with CNs.
基金Supported by the National Science Foundation of Iran
文摘Herein a novel aminopropyl-containing ionic liquid based organosilica(ILOS-NH_2) is prepared, characterized and applied as effective adsorbent for removal of crystal violet(CV) dye from wastewater. The ILOS-NH2 material was synthesized by hydrolysis and co-condensation of 1,3-bis-(3-trimethoxysilylpropyl)-imidazolium chloride(BTMSPIC) under acidic conditions followed by treatment with 3-aminopropyl-trimethoxysilane in toluene under reflux conditions. This material was characterized using scanning electron microscopy(SEM), diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS), thermal gravimetric analysis(TGA) and energy dispersive X-ray analysis(EDAX). The material was effectively used in the removal of crystal violet at ambient temperature and showed high capacity and stability under applied conditions. The efficacy of p H, contact time, adsorbent dose, initial dye concentration, temperature, and isotherm studies and the applicability of pseudo-first, second order and Elovich kinetic models have also been investigated.
基金Guangdong Basic and Applied Basic Research Found ation(Guangdong Province,China)general project for the financial support。
文摘Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such as high ionic conductivity,non-flammability,and plasticity.Various nuclear magnetic resonance(NMR)spectroscopy techniques including solid-state NMR,pulsed-field gradient(PFG)NMR,and magnetic resonance imaging(MRI)etc.,provide us a versatile toolkit to understand the fundamental level structures,molecular dynamics,and ionic interactions in these materials.This article reviews the commonly used NMR methods including solid-and solution-state NMR,PFG-NMR,dynamic nuclear polarization(DNP)and the application of these methods in revealing the microscopic level structures and ion-transport mechanisms in OIPC materials.
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.
文摘The title compound, [Nd(dmso) 7Cl][Bph 4] 2(dmso=dimethylsulfoxide, Bph 4=tetraphenylboron anion) was synthesized in organic solvent acetone/EtOH and the structure was determined by single crystal X ray diffraction. The crystal is triclinic with space group P 1, and the crystal data are as follows: a =1 2554(1) nm, b = 1 2799(1) nm, c =2 4598(3) nm; α =93 53(1)°, β =104 50(1)°, γ =112 77(1)°, V =3 4722(6) nm 3, Z =2, M r=1365 01, D c=1 306 g·cm -3 . The crystal is composed of a big cation [Nd(dmso) 7Cl] 2+ and two big anions [BPh 4] -. The Nd 3+ is coordinated by a chlorine atom and seven oxygen atoms from seven dimethylsulfoxides forming a distorted square antiprism coordination polyhedron,while the BPh - 4 anion is charge equilibrium ion.
基金supported by National Natural Science Foundation of China(No.22371278)Funding of Fujian Provincial Chemistry Discipline Alliance+1 种基金Natural Science Foundation of Fujian Province(No.2021J06035)Youth Innovation Promotion Association CAS(No.Y2018081)。
文摘For a long time,researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates(POMs).Modifying POMs with various types and properties of metals has broadened their applications in fields such as magnetism,luminescence,and catalysis.However,despite the discovery of numerous POM structures doped with transition metal ions,the development of aluminum(Al)as aⅢA group metal in the POM field has been slow.Aluminum,the most abundant metal in nature,offers innate electron-deficient properties that,when combined with highly charged POMs,could introduce novel structures and excellent functionalities like proton conduction to this field.Therefore,this review will address the gap in summarizing Al-containing POMs by categorizing and summarizing the synthesis,structural characteristics,and properties of Al-containing POMs,aiming to provide a theoretical foundation for exploring POM structures doped with Al atoms.The review also analyzes and forecasts the prospects in this field.
