The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclin...The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.展开更多
Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries(PIBs)because of their abundant,recyclable and highly customizable characteristics.Howe...Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries(PIBs)because of their abundant,recyclable and highly customizable characteristics.However,small molecular organics are easily solubilized in organic electrolytes,resulting in a low capacity and poor stability.Herein,the folic acid-based supermolecules(SM-FAs)are successfully prepared by a hydrothermal assisted self-assembly strategy.Due to multi-locus hydrogen bonds(HBs)and the cyclizedπ-conjugated interactions,the structural stability of SM-FAs has been significantly improved,and the solubility in carbonate electrolytes has been effectively inhibited.As an anode for PIB,the SM-FA-6sample exhibits a large capacity(206 mAh/g at 50 mA/g)and an outstanding cycle stability(capacity retention of 91%after 1000 cycles at 50 m A/g).More impressively,an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K^(+),and the atypicalπ–K^(+)interaction within the assembled conjugation framework,is unraveled for potassium ion accumulation.It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.展开更多
The interaction of beta-cyclodextrin(beta-CD), hydroxypropyl-beta-CD and gamma-CD with the drug rutin has been investigated by using fluorimetry. The stoichiometry of the complexes and their formation constants have b...The interaction of beta-cyclodextrin(beta-CD), hydroxypropyl-beta-CD and gamma-CD with the drug rutin has been investigated by using fluorimetry. The stoichiometry of the complexes and their formation constants have been estimated. The thermodynamic parameters for the formation of complexes were obtained. The complexing ability of HP-beta-CD is remarkably stronger than beta-CD and gamma-CD.展开更多
Viologen,as a type of strong electron acceptor,is prone to undergo electron transfer(ET)and change color under external stimuli.However,due to the easy aggrega-tion of viologen molecules,they usually suffer from poorfl...Viologen,as a type of strong electron acceptor,is prone to undergo electron transfer(ET)and change color under external stimuli.However,due to the easy aggrega-tion of viologen molecules,they usually suffer from poorfluorescence emission in the condensed phase.Herein,a new viologen derivative of VioCl_(2)⋅2Cl(1^(2+)⋅2Cl)was designed and synthesized,in which thefluorescence was enhanced by intro-ducing Me-β-CD to weaken the interactions between viologen molecules.Then a viologen-based host-vip supramolecule of 1^(2+)@Me-β-CD was obtained by elec-trostatic interactions.Photo-/chemo-responded vip 1^(2+)supplies 1^(2+)@Me-β-CD,a green and dark purple caused by intramolecular and intermolecular ET.Further-more,1^(2+)@Me-β-CD displays an additional thermal responsive purple color.The triple chromic behaviors all exhibit excellent reversibility and cycling stability.As expected,1^(2+)@Me-β-CD exhibits strong photoluminescence(PL)in solid-liquid dual states,presenting an improved quantum yield(Φ)from 1^(2+)(Φ_(s)=0.37%,Φ_(1)= 16.74%)to=1^(2+)@Me-β-CD(Φ_(s)= 10.45%,Φ_(1)= 25.86%),and thefluores-=cence intensity can be dynamically modulated by light,heat,and acid/base vapors.The multi-responsive chromism and tunablefluorescence of 1^(2+)@Me-β-CD allow for potential applications in information security and smart windows.展开更多
The solubility and stability of platinum-based anticancer agents have a direct bearing on their activity and toxicity.Much research has been conducted over the past decades in order to prepare drugs such as cisplatin ...The solubility and stability of platinum-based anticancer agents have a direct bearing on their activity and toxicity.Much research has been conducted over the past decades in order to prepare drugs such as cisplatin and carboplatin with improved efficacy and reduced toxicity.Based on the premise that supramolecular platinum agents may have superior physicochemical properties,we successfully designed a novel anticancer agent,dicycloplatin,which has proven to be active against a number of human malignancies.The crystal structure of dicycloplatin has been determined.An aqueous solution of dicycloplatin was also studied using electrospray ionization mass spectrometry (ESI-MS).Based on the experimental observations,a model of the structure in aqueous solution is proposed which explains both the higher solubility and higher stability of dicycloplatin compared with carboplatin.展开更多
Dimethyl 4,6-bis(bromomethyl)isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styre...Dimethyl 4,6-bis(bromomethyl)isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styrene successfully.Results showed that the process had some of the good characteristics of controlled/living free radical poly-merization.The molecular weight of the obtained polymer increased linearly with monomer conversion,its molecular weight distribution was very narrow,and a linear relationship between ln([M]0/[M])and polymerization time was found.A well-defined novel structural polystyrene containing two ester groups in the mid-main chain was prepared with con-trolled molecular weight and narrow polydispersity.The structure of the polymer was confirmed by 1H-NMR spectra.After being hydrolyzed,dicarboxy polystyrene was obtained and used to form ionic-bonded supramolecules with 1-dodecanamine as a model of the star-shaped supramolecules.The supramolecules formed were characterized by Fourier transform infrared(FTIR)spectrum.展开更多
In the absence of inorganic anion templates and in high pH condition(pH∼14),an unprecedented carbonate-hydrate supramolecule,[(CO_(3))_(2)(H_(2)O)]^(4−),trapped from atmospheric CO_(2),found to play an anion templati...In the absence of inorganic anion templates and in high pH condition(pH∼14),an unprecedented carbonate-hydrate supramolecule,[(CO_(3))_(2)(H_(2)O)]^(4−),trapped from atmospheric CO_(2),found to play an anion templating role to support the architecture of two related silver(Ag)nanoclusters(SD/Ag54a and SD/Ag55a),which are coprotected by the same organic ligands but differ by one silver atom of the metallic frameworks.Two[(CO_(3))_(2)(H_(2)O)]^(4−)supramolecules are trapped into two Ag/tBuPhS/dppm pods,connected by a pair of face-shared silver pentagonal bipyramids(Ag_(11))into peanut-shaped silver nanoclusters.Interestingly,the equatorial Ag_(11) kernel represents a new embryonic ultrasmall silver nanocluster that is thought to follow a special facesharing growth fashion from pentagonal bipyramidal Ag7 subunit,which is also structurally elucidated in another new Ag44 nanocluster(SD/Ag44c)obtained in similar assembly system just changing tBuPhS−to iPrPhS−ligand.The isolation of SD/Ag54a and SD/Ag55a were associated with:(1)supramolecule induction and(2)reductive and carbonate-rich assembly system.First,this work brings a fresh perspective on the role of carbonate-water anion supramolecule in directing the assembly of silver nanoclusters.Second,it realizes the control of reduction kinetics and kernel growth using multiple weak reductants and thiolate ligands.Third,it provides a possible face-shared growth route for ultrasmall silver nanoclusters.展开更多
Two photolabile amphiphilic supramolecules were designed and synthesized with mono-dendrite and tri-dendrite, which can reversibly self-assemble to spheroid and wedge-shaped nanoparticles. With multiple branches of te...Two photolabile amphiphilic supramolecules were designed and synthesized with mono-dendrite and tri-dendrite, which can reversibly self-assemble to spheroid and wedge-shaped nanoparticles. With multiple branches of terminal amine labeled PEG, these nanoparticles can associate with a negatively charged oligonucleotide and their usage for oligonucleotide delivery was evaluated. Oligonucleotide/nanoparticle complex containing tri-dendrite can efficiently deliver oligonucleotide into cells via endocytosis, while the complex containing mono-dendrite almost lost their ability to deliver oligonucleotide. Further light activation triggered the dissociation of tri-dendrite supramolecular assembly via 1,4- and 1,6-quinone-methide rearrangement, leading to the efficient unpacking of the oligonucleotide in cells.展开更多
Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem ...Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem crossing(ISC) and suppressing non-radiative transitions. In supramolecular chemistry, the control and regulation of molecular recognition based on the role of the host and vip in supramolecular polymers matrix, has attracted much attention. Recently, researchers have successfully achieved room temperature phosphorescence of pure organic complexes through host-vip interactions. The host molecule specifically includes the phosphorescent vip to reduce non-radiative transitions and enhance room temperature phosphorescence emission. This review aims to describe the developments and achievements of pure organic room temperature phosphorescence systems through the mechanism of host-vip interactions in recent years, and demonstrates the exploration and pursuit of phosphorescent materials of researchers in different fields.展开更多
A novel supramolecular compound, [Co(IN)_2(H_2O)_4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Thoug...A novel supramolecular compound, [Co(IN)_2(H_2O)_4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Though the unit cell structure of the title compound is only monomeric, all these units as building blocks are assembled into a novel three-dimensional supramolecular network via the widely hydrogen-bonding and π-π stacking interactions.展开更多
Phase transition and phase separation of formamidinium-cesium(FA-Cs)perovskite during the fabrication and operation processes reduce the efficiency and stability of perovskite solar cells(PSCs).Here,we develop an in s...Phase transition and phase separation of formamidinium-cesium(FA-Cs)perovskite during the fabrication and operation processes reduce the efficiency and stability of perovskite solar cells(PSCs).Here,we develop an in situ molecular self-assembly approach on perovskite surface using an amine nickel porphyrin(NiP).The NiP doped perovskite precursor solution was deposited on substrate by blade-coating under ambient condition.NiP molecules self-assemble into supramolecule bound on perovskite surface during the vacuum-assisted process.Such a modification controls the perovskite grain growth to generate the uniform perovskite film.The supramolecule can release the residual lattice strain to inhibit the phase transition of perovskite film,and promote the charge extraction and transport to suppress the phase separation of FA-Cs perovskite during long-term illumination condition.Consequently,the best efficiency of large-area NiP-based FA-Cs-PSCs with the active area of 1.0 cm2 is up to 20.3%(certified as 19.2%),which is close to the record efficiency(20.37%)by blade-coating.Unencapsulated NiP-doped device reveals the remarkably improved overall stabilities.This work affords a novel way to address the phase transition and phase separation in FA-Cs perovskite.展开更多
Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emi...Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emission spectra.The crystal structures were determined with single crystal X-ray diffraction method.The two compounds were isostructural,and 3D supramolecule architectures were formed by hydrogen bonds and π-π stacking interactions.They strongly emitted upon excitation due to π→π transition of th...展开更多
A novel two-dimensional supramolecular complex [Mn（phen）（DPZDA）（H2O）]·2H2O has been synthesized by the reaction of Mn（CH3COO）2, 1,10-phenanthroline （phen） and H2DPZDA （3,5-dimethyl-pyrazine-2,6-dicarbo...A novel two-dimensional supramolecular complex [Mn（phen）（DPZDA）（H2O）]·2H2O has been synthesized by the reaction of Mn（CH3COO）2, 1,10-phenanthroline （phen） and H2DPZDA （3,5-dimethyl-pyrazine-2,6-dicarboxylic acid）. Elemental analysis, IR spectra and X-ray singlecrystal diffraction were carried out to determine the composition and crystal structure of the title complex. Crystal data： triclinic system, space group P1, a = 7.7474（13）, b = 9.3381（15）, c = 15.146（3） A, α = 93.872（3）, β= 102.451 （11 ）, y = 105.261 （ 11）°, C20H20MnN4O7, Mr = 483.34, Z = 2, F（000） = 498, V=1023.2（3）A^3, Dc=1.569 g/cm^3,μ=0.697 mm^-1, -9≤h≤9, -11≤k≤10, -18≤l≤12, R = 0.0365 and wR=0.0901 for 3585 independent reflections （Rint= 0.0165） and 2923 observed reflections （I〉 2σ（I））. Structural analysis indicates that Mn（Ⅱ） adopts a distorted octahedral geometry. The 2-D framework supramolecular structure of the title complex is constructed from hydrogen bonds and π…π interactions.展开更多
Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons...Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons could enhance their reversible capacities.Nevertheless,most lignocellulose biomasses lack heteroatoms,making it a challenge to design highly heteroatom-doped carbons(>10 at%).Herein,we report a new preparation strategy for amorphous carbon anodes.Nitrogen/sulfur co-doped lignin-derived porous carbons(NSLPC)with ultra-high nitrogen doping levels(21.6 at%of N and 0.8 at%of S)from renewable lignin biomacromolecule precursors were prepared through a supramolecule-mediated pyrolysis strategy.This supermolecule/lignin composite decomposes forming a covalently bonded graphitic carbon/amorphous carbon intermediate product,which induces the formation of high heteroatom doping in the obtained NSLPC.This unique pyrolysis chemistry and high heteroatom doping of NSLPC enable abundant defective active sites for the adsorption of K+and improved kinetics.The NSLPC anode delivered a high reversible capacity of 419 mAh g^(-1)and superior cycling stability(capacity retention of 96.6%at 1 A g^(-1)for 1000 cycles).Potassiumion hybrid capacitors assembled by NSLPC anode exhibited excellent cycling stability(91%capacity retention for 2000 cycles)and a high energy density of 71 Wh kg^(-1)at a power density of 92 W kg^(-1).展开更多
The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic ...The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic parameters: a = 7.4161(2), b = 8.1754(3), c = 10.7545(4) ? a = 92.958(2), b = 109.978(1), g = 93.369(2)? V = 609.96(4) ?, C20H20N10CuO8, Mr = 592.00, Dc = 1.612 g/cm3, m(MoKa) = 0.964 mm-1, F(000) = 303, Z = 1, the final R = 0.0494 and wR = 0.1269 for 1945 observed reflections (I > 2s(I)). X-ray analysis reveals that the Cu atom adopts a distorted octahedral (4 + 2) coordination. The four closer donor atoms include two N atoms of 3,3?azpy and two O atoms of the coordination aqua with the CuN and CuO distances of 2.014(3) and 1.974(3) ? respectively. Two longer out-of-plane CuO bonds (2.450(3) ? from nitrate complete the strongly distorted octahedral coordination of the Cu atom. Hydrogen bonds are formed through H atoms of each coordination aqua with the remaining N atoms of 3,3?azpy and O atoms of nitrate. A two-dimensional network is constructed by hydrogen bonds and p-p interactions.展开更多
A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analys...A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex： monoclinic, space group C2/c, a = 19.214（3）, b = 10.6973（14）, c = 22.567（3） A, β = 105.081（2）°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F（000） = 2160, V= 4478.6（10） A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 （Rint = 1.0357） independent reflections and 3290 observed ones （I 〉 2σ（I））. Structural analysis shows that coordination geometry of Cu（ Ⅱ ） is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.展开更多
Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramol...Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramolecular explosive was investigated by the molecular dynamic (MD) method. Interaction between oxygen atoms in HMX and hydrogen atoms in NTO or between hydrogen atoms in HMX and oxygen atoms in NTO were studied by the radial distribution function (RDF). It shows that there are strong hydrogen bonds and Van Der Waals forces between HMX and NTO, in which the hydrogen bonds between oxygen atoms in the NTO and hydrogen atoms in HMX are the main host-vip interactions. The distributions of bond length, bond angle and dihedral angle were simulated by MD. It shows that the structure of HMX is seriously distorted. The binding energies and X-ray powder diffraction (XRD) patterns were calculated on the basis of the final HMX/NTO supramolecular structures. The results show that the binding energies of six supramolecular models are E binding (1 1 1-) >E binding (1 0 0)>E binding (0 2 0)>E binding (random)>E binding (1 0 2-)>Ebinding (0 1 1), and the XRD patterns of six supramolecular models are quite different from pure HMX or NTO. Based on the investigation for growth morphology, binding energies and RDF, the model of HMX supercell substituted by NTO along the (1 1 1-) surface of HMX is easier to form.展开更多
Fluorescent vesicles have recently attracted increasing attention because of their potential applications in bioimaging,diagnostics, and theranostics, for example, in vivo study of the delivery and the distribution of...Fluorescent vesicles have recently attracted increasing attention because of their potential applications in bioimaging,diagnostics, and theranostics, for example, in vivo study of the delivery and the distribution of active substances. However, fluorescent vesicles containing conventional organic dyes often suffer from the problem of aggregation-caused quenching(ACQ) of fluorescence.Fluorescent vesicles working with aggregation-induced emission(AIE) offer an extraordinary tool to tackle the ACQ issue, showing advantages such as high emission efficiency, superior photophysical stability, low background interference, and high sensitivity. AIE fluorescent vesicles represent a new type of fluorescent and functional nanomaterials. In this review, we summarize the recent advances in the development of AIE fluorescent vesicles. The review is organized according to the chemical structures and architectures of the amphiphilic molecules that constitute the AIE vesicles, i.e., small-molecule amphiphiles, amphiphilic polymers, and amphiphilic supramolecules and supramacromolecules. The studies on the applications of these AIE vesicles as stimuli-responsive vesicles,fluorescence-guided drug release carriers, cell imaging tools, and fluorescent materials based on fluorescence resonance energy transfer(FRET) are also discussed.展开更多
A new dinuclear centrosymmetric complex [LaL（HL）（H2O）3]2（2H2O （H2L = 3-nitrophthalic acid, NPA） was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The com...A new dinuclear centrosymmetric complex [LaL（HL）（H2O）3]2（2H2O （H2L = 3-nitrophthalic acid, NPA） was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The complex crystallizes in triclinic system, space group P1^- with a = 8.1549（16）, b = 8.8856（18）, c = 15.277（3）A,α= 100.93（3）,α= 90.81（3）, γ= 104.56（3）°, V = 1049.8（4）A^3, Z = 1,μ= 2.125 mm^-1, Dc=1.994 g/cm^3, R = 0.0259 and wR = 0.0679. Two 3-nitrophthalates（2-） coordinate with the La3＋ ions in a bridging mode, and two monohydrogen- 3-nitrophthates（1-） and three waters in terminal ways, respectively. Each La^3＋ ion is nine-coordinated to exhibit a distorted tricapped trigonal prism coordination polyhedron. Both the coordinated and crystal waters are involved in the inter- and intramolecular hydrogen bonds. The dinuclear units are linked into a 2D network structure in the ab plane via intermolecular hydrogen bonds along the axes a and b. Two crystal waters fill each rhombic pore of the network. The networks are further packed along the c axis forming a layered supramolecular structure through the C-H…O weak forces between the adjacent sheets. TGA analysis shows the complex undergoes the loss of waters of crystallization and coordination and the decomposition of ligands sequentially.展开更多
基金Supported by the Education Comm ission of Zhejiang Province(No. 2 0 0 10 12 9) and " 5 5 1" Distinguished PersonFoundation of Wenzhou.
文摘The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.
基金the financially supported by the “Western Light”Foundation of Chinese Academy of Sciences(No.2019XBQNXZ-A-002)the Youth Innovation Promotion Association,Chinese Academy of Sciences(No.2019427)+1 种基金the Xinjiang Science Foundation for Distinguished Young Scholars(No.2019Q004)the Key Research and Development Projects of Xinjiang Uygur Autonomous Region(Nos.2022B02013 and 2022B01023)。
文摘Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries(PIBs)because of their abundant,recyclable and highly customizable characteristics.However,small molecular organics are easily solubilized in organic electrolytes,resulting in a low capacity and poor stability.Herein,the folic acid-based supermolecules(SM-FAs)are successfully prepared by a hydrothermal assisted self-assembly strategy.Due to multi-locus hydrogen bonds(HBs)and the cyclizedπ-conjugated interactions,the structural stability of SM-FAs has been significantly improved,and the solubility in carbonate electrolytes has been effectively inhibited.As an anode for PIB,the SM-FA-6sample exhibits a large capacity(206 mAh/g at 50 mA/g)and an outstanding cycle stability(capacity retention of 91%after 1000 cycles at 50 m A/g).More impressively,an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K^(+),and the atypicalπ–K^(+)interaction within the assembled conjugation framework,is unraveled for potassium ion accumulation.It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.
文摘The interaction of beta-cyclodextrin(beta-CD), hydroxypropyl-beta-CD and gamma-CD with the drug rutin has been investigated by using fluorimetry. The stoichiometry of the complexes and their formation constants have been estimated. The thermodynamic parameters for the formation of complexes were obtained. The complexing ability of HP-beta-CD is remarkably stronger than beta-CD and gamma-CD.
基金National Natural Science Foundation of China,Grant/Award Numbers:21571126,62271299Shanghai Key Laboratory of High Temperature Superconductors。
文摘Viologen,as a type of strong electron acceptor,is prone to undergo electron transfer(ET)and change color under external stimuli.However,due to the easy aggrega-tion of viologen molecules,they usually suffer from poorfluorescence emission in the condensed phase.Herein,a new viologen derivative of VioCl_(2)⋅2Cl(1^(2+)⋅2Cl)was designed and synthesized,in which thefluorescence was enhanced by intro-ducing Me-β-CD to weaken the interactions between viologen molecules.Then a viologen-based host-vip supramolecule of 1^(2+)@Me-β-CD was obtained by elec-trostatic interactions.Photo-/chemo-responded vip 1^(2+)supplies 1^(2+)@Me-β-CD,a green and dark purple caused by intramolecular and intermolecular ET.Further-more,1^(2+)@Me-β-CD displays an additional thermal responsive purple color.The triple chromic behaviors all exhibit excellent reversibility and cycling stability.As expected,1^(2+)@Me-β-CD exhibits strong photoluminescence(PL)in solid-liquid dual states,presenting an improved quantum yield(Φ)from 1^(2+)(Φ_(s)=0.37%,Φ_(1)= 16.74%)to=1^(2+)@Me-β-CD(Φ_(s)= 10.45%,Φ_(1)= 25.86%),and thefluores-=cence intensity can be dynamically modulated by light,heat,and acid/base vapors.The multi-responsive chromism and tunablefluorescence of 1^(2+)@Me-β-CD allow for potential applications in information security and smart windows.
文摘The solubility and stability of platinum-based anticancer agents have a direct bearing on their activity and toxicity.Much research has been conducted over the past decades in order to prepare drugs such as cisplatin and carboplatin with improved efficacy and reduced toxicity.Based on the premise that supramolecular platinum agents may have superior physicochemical properties,we successfully designed a novel anticancer agent,dicycloplatin,which has proven to be active against a number of human malignancies.The crystal structure of dicycloplatin has been determined.An aqueous solution of dicycloplatin was also studied using electrospray ionization mass spectrometry (ESI-MS).Based on the experimental observations,a model of the structure in aqueous solution is proposed which explains both the higher solubility and higher stability of dicycloplatin compared with carboplatin.
基金supported by the National Natural Science Foundation of China(Grant No.20474059)Specialized Research Fund for the Doctoral Program of Higher Education(Grant No.20040358017).
文摘Dimethyl 4,6-bis(bromomethyl)isophthalate was synthesized by bromomethylation,oxidation,esterification and bromination of 1,3-dimethylbenzene.This was used to initiate the atom transfer radical polymerization of styrene successfully.Results showed that the process had some of the good characteristics of controlled/living free radical poly-merization.The molecular weight of the obtained polymer increased linearly with monomer conversion,its molecular weight distribution was very narrow,and a linear relationship between ln([M]0/[M])and polymerization time was found.A well-defined novel structural polystyrene containing two ester groups in the mid-main chain was prepared with con-trolled molecular weight and narrow polydispersity.The structure of the polymer was confirmed by 1H-NMR spectra.After being hydrolyzed,dicarboxy polystyrene was obtained and used to form ionic-bonded supramolecules with 1-dodecanamine as a model of the star-shaped supramolecules.The supramolecules formed were characterized by Fourier transform infrared(FTIR)spectrum.
基金This work was financially supported by the National Natural Science Foundation of China(grant nos.21822107,21571115,21827801,and 21671172)the Natural Science Foundation of Shandong Province(nos.JQ201803 and ZR2017 MB061)the Taishan Scholar Project of Shandong Province of China,and the Qilu Youth Scholar Funding of Shandong University and the Fundamental Research Funds of Shandong University(104.205.2.5).
文摘In the absence of inorganic anion templates and in high pH condition(pH∼14),an unprecedented carbonate-hydrate supramolecule,[(CO_(3))_(2)(H_(2)O)]^(4−),trapped from atmospheric CO_(2),found to play an anion templating role to support the architecture of two related silver(Ag)nanoclusters(SD/Ag54a and SD/Ag55a),which are coprotected by the same organic ligands but differ by one silver atom of the metallic frameworks.Two[(CO_(3))_(2)(H_(2)O)]^(4−)supramolecules are trapped into two Ag/tBuPhS/dppm pods,connected by a pair of face-shared silver pentagonal bipyramids(Ag_(11))into peanut-shaped silver nanoclusters.Interestingly,the equatorial Ag_(11) kernel represents a new embryonic ultrasmall silver nanocluster that is thought to follow a special facesharing growth fashion from pentagonal bipyramidal Ag7 subunit,which is also structurally elucidated in another new Ag44 nanocluster(SD/Ag44c)obtained in similar assembly system just changing tBuPhS−to iPrPhS−ligand.The isolation of SD/Ag54a and SD/Ag55a were associated with:(1)supramolecule induction and(2)reductive and carbonate-rich assembly system.First,this work brings a fresh perspective on the role of carbonate-water anion supramolecule in directing the assembly of silver nanoclusters.Second,it realizes the control of reduction kinetics and kernel growth using multiple weak reductants and thiolate ligands.Third,it provides a possible face-shared growth route for ultrasmall silver nanoclusters.
基金National Natural Science Foundation of China(Grant No.21372018)the National Basic Research Program of China(973 Program,Grant No.2013CB933800)+1 种基金Program for New Century Excellent Talents in University(Grant No.NCET-10-0203)the State Key Laboratory of Pharmaceutical Biotechnology(Grant No.KF-GN-201305)
文摘Two photolabile amphiphilic supramolecules were designed and synthesized with mono-dendrite and tri-dendrite, which can reversibly self-assemble to spheroid and wedge-shaped nanoparticles. With multiple branches of terminal amine labeled PEG, these nanoparticles can associate with a negatively charged oligonucleotide and their usage for oligonucleotide delivery was evaluated. Oligonucleotide/nanoparticle complex containing tri-dendrite can efficiently deliver oligonucleotide into cells via endocytosis, while the complex containing mono-dendrite almost lost their ability to deliver oligonucleotide. Further light activation triggered the dissociation of tri-dendrite supramolecular assembly via 1,4- and 1,6-quinone-methide rearrangement, leading to the efficient unpacking of the oligonucleotide in cells.
基金financial support from the National Natural Science Foundation of China (NSFC) (Nos. 21788102, 21722603 and 21871083)Project supported by Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03)+2 种基金the Innovation Program of Shanghai Municipal Education Commission (No. 2017-01-07-00-02-E00010)State Key Laboratory for Modification of Chemical Fibers and Polymer Materials (No. KF1803)Donghua University and the Fundamental Research Funds (No. KF1803) for the Central Universities
文摘Pure organic room temperature phosphorescence(RTP) has been attracting a lot interest recently. So far,many strategies have succeeded in achieving efficient organic RTP materials by increasing the rate of intersystem crossing(ISC) and suppressing non-radiative transitions. In supramolecular chemistry, the control and regulation of molecular recognition based on the role of the host and vip in supramolecular polymers matrix, has attracted much attention. Recently, researchers have successfully achieved room temperature phosphorescence of pure organic complexes through host-vip interactions. The host molecule specifically includes the phosphorescent vip to reduce non-radiative transitions and enhance room temperature phosphorescence emission. This review aims to describe the developments and achievements of pure organic room temperature phosphorescence systems through the mechanism of host-vip interactions in recent years, and demonstrates the exploration and pursuit of phosphorescent materials of researchers in different fields.
基金Supported by the National Natural Science Foundation of China( No.2 973 3 0 90 ),the Research Funds for the DoctoralProgram of Higher Education,the State Key L aboratory of Coordination ChemistryNanjing U niversity and the Funds ofInner Mongolia Edu
文摘A novel supramolecular compound, [Co(IN)_2(H_2O)_4](1), was synthesized by means of the hydrothermal method and its structure was characterized with elemental analysis, FT-IR spectrum, TGA and X-ray diffraction. Though the unit cell structure of the title compound is only monomeric, all these units as building blocks are assembled into a novel three-dimensional supramolecular network via the widely hydrogen-bonding and π-π stacking interactions.
基金We acknowledge the National Natural Science Foundation of China(No.22075116)Fundamental Research Funds for the Central Universities of China(No.lzujbky-2021-ey10)Science and Technology program of Gansu Province(No.20JR5RA305).
文摘Phase transition and phase separation of formamidinium-cesium(FA-Cs)perovskite during the fabrication and operation processes reduce the efficiency and stability of perovskite solar cells(PSCs).Here,we develop an in situ molecular self-assembly approach on perovskite surface using an amine nickel porphyrin(NiP).The NiP doped perovskite precursor solution was deposited on substrate by blade-coating under ambient condition.NiP molecules self-assemble into supramolecule bound on perovskite surface during the vacuum-assisted process.Such a modification controls the perovskite grain growth to generate the uniform perovskite film.The supramolecule can release the residual lattice strain to inhibit the phase transition of perovskite film,and promote the charge extraction and transport to suppress the phase separation of FA-Cs perovskite during long-term illumination condition.Consequently,the best efficiency of large-area NiP-based FA-Cs-PSCs with the active area of 1.0 cm2 is up to 20.3%(certified as 19.2%),which is close to the record efficiency(20.37%)by blade-coating.Unencapsulated NiP-doped device reveals the remarkably improved overall stabilities.This work affords a novel way to address the phase transition and phase separation in FA-Cs perovskite.
文摘Two three-dimensional complexes Ln(DMPA)3phen2(HDMPA=3,4-dimet hoxyphenylacetic acid,homoveratric acid;Ln=La,Y;phen=1,10-phenanthroline) were synthesized under hydrothermal conditions and characterized with IR and emission spectra.The crystal structures were determined with single crystal X-ray diffraction method.The two compounds were isostructural,and 3D supramolecule architectures were formed by hydrogen bonds and π-π stacking interactions.They strongly emitted upon excitation due to π→π transition of th...
基金Project supported by the Natural Science Foundation of Liaoning Province (No. 20052014) and Doctor Foundation of Shenyang Institute of Chemical Technology (No. 20063204)
文摘A novel two-dimensional supramolecular complex [Mn（phen）（DPZDA）（H2O）]·2H2O has been synthesized by the reaction of Mn（CH3COO）2, 1,10-phenanthroline （phen） and H2DPZDA （3,5-dimethyl-pyrazine-2,6-dicarboxylic acid）. Elemental analysis, IR spectra and X-ray singlecrystal diffraction were carried out to determine the composition and crystal structure of the title complex. Crystal data： triclinic system, space group P1, a = 7.7474（13）, b = 9.3381（15）, c = 15.146（3） A, α = 93.872（3）, β= 102.451 （11 ）, y = 105.261 （ 11）°, C20H20MnN4O7, Mr = 483.34, Z = 2, F（000） = 498, V=1023.2（3）A^3, Dc=1.569 g/cm^3,μ=0.697 mm^-1, -9≤h≤9, -11≤k≤10, -18≤l≤12, R = 0.0365 and wR=0.0901 for 3585 independent reflections （Rint= 0.0165） and 2923 observed reflections （I〉 2σ（I））. Structural analysis indicates that Mn（Ⅱ） adopts a distorted octahedral geometry. The 2-D framework supramolecular structure of the title complex is constructed from hydrogen bonds and π…π interactions.
基金the financial support from the National Natural Science Foundation of China(22108044,22208061)the Research and Development Program in Key Fields of Guangdong Province(2020B1111380002)+1 种基金the Basic Research and Applicable Basic Research in Guangzhou City(202201010290)the financial support from the Guangdong Provincial Key Laboratory of Plant Resources Biorefinery(2021GDKLPRB07)。
文摘Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons could enhance their reversible capacities.Nevertheless,most lignocellulose biomasses lack heteroatoms,making it a challenge to design highly heteroatom-doped carbons(>10 at%).Herein,we report a new preparation strategy for amorphous carbon anodes.Nitrogen/sulfur co-doped lignin-derived porous carbons(NSLPC)with ultra-high nitrogen doping levels(21.6 at%of N and 0.8 at%of S)from renewable lignin biomacromolecule precursors were prepared through a supramolecule-mediated pyrolysis strategy.This supermolecule/lignin composite decomposes forming a covalently bonded graphitic carbon/amorphous carbon intermediate product,which induces the formation of high heteroatom doping in the obtained NSLPC.This unique pyrolysis chemistry and high heteroatom doping of NSLPC enable abundant defective active sites for the adsorption of K+and improved kinetics.The NSLPC anode delivered a high reversible capacity of 419 mAh g^(-1)and superior cycling stability(capacity retention of 96.6%at 1 A g^(-1)for 1000 cycles).Potassiumion hybrid capacitors assembled by NSLPC anode exhibited excellent cycling stability(91%capacity retention for 2000 cycles)and a high energy density of 71 Wh kg^(-1)at a power density of 92 W kg^(-1).
基金the funds of the Key Laboratory of Organic Syntheses of Jiansu province, and the funds of the State Key Laboratory of Structural Chemistry
文摘The title complex [Cu(NO3)2(H2O)2(3,3-azpy)2] (3,3?azpy = 3,3?azobispyridine) has been synthesized and characterized, and its crystal belongs to the triclinic system, space group P with the following crystallographic parameters: a = 7.4161(2), b = 8.1754(3), c = 10.7545(4) ? a = 92.958(2), b = 109.978(1), g = 93.369(2)? V = 609.96(4) ?, C20H20N10CuO8, Mr = 592.00, Dc = 1.612 g/cm3, m(MoKa) = 0.964 mm-1, F(000) = 303, Z = 1, the final R = 0.0494 and wR = 0.1269 for 1945 observed reflections (I > 2s(I)). X-ray analysis reveals that the Cu atom adopts a distorted octahedral (4 + 2) coordination. The four closer donor atoms include two N atoms of 3,3?azpy and two O atoms of the coordination aqua with the CuN and CuO distances of 2.014(3) and 1.974(3) ? respectively. Two longer out-of-plane CuO bonds (2.450(3) ? from nitrate complete the strongly distorted octahedral coordination of the Cu atom. Hydrogen bonds are formed through H atoms of each coordination aqua with the remaining N atoms of 3,3?azpy and O atoms of nitrate. A two-dimensional network is constructed by hydrogen bonds and p-p interactions.
基金Project supported by the National Natural Science Foundation of China (No. 20671064)Foundation of Education Committee of Liaoning Province (No. 2005336)
文摘A binuclear complex [Cu2（phen）2（ip）（Hip）2].4H2O has been synthesized by the reaction of Cu（CH3COO）2.H2O, phen（1,10-phenanthroline） and isophthalic acid （H2ip） under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure. Crystal data for this complex： monoclinic, space group C2/c, a = 19.214（3）, b = 10.6973（14）, c = 22.567（3） A, β = 105.081（2）°, C24H19N2O8Cu, Mr= 526.95, Z = 8, F（000） = 2160, V= 4478.6（10） A3, Dc = 1.563 g/cm^3,μ = 1.030 mm^-1, -24≤h≤ 16, -13≤k≤13, -28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 （Rint = 1.0357） independent reflections and 3290 observed ones （I 〉 2σ（I））. Structural analysis shows that coordination geometry of Cu（ Ⅱ ） is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.
基金Sponsored by the National Natural Science Foundation of China (61106078)NUST Research Funding (2011ZDJH28)
文摘Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramolecular explosive was investigated by the molecular dynamic (MD) method. Interaction between oxygen atoms in HMX and hydrogen atoms in NTO or between hydrogen atoms in HMX and oxygen atoms in NTO were studied by the radial distribution function (RDF). It shows that there are strong hydrogen bonds and Van Der Waals forces between HMX and NTO, in which the hydrogen bonds between oxygen atoms in the NTO and hydrogen atoms in HMX are the main host-vip interactions. The distributions of bond length, bond angle and dihedral angle were simulated by MD. It shows that the structure of HMX is seriously distorted. The binding energies and X-ray powder diffraction (XRD) patterns were calculated on the basis of the final HMX/NTO supramolecular structures. The results show that the binding energies of six supramolecular models are E binding (1 1 1-) >E binding (1 0 0)>E binding (0 2 0)>E binding (random)>E binding (1 0 2-)>Ebinding (0 1 1), and the XRD patterns of six supramolecular models are quite different from pure HMX or NTO. Based on the investigation for growth morphology, binding energies and RDF, the model of HMX supercell substituted by NTO along the (1 1 1-) surface of HMX is easier to form.
基金financially supported by the French National Research Agency (No. ANR-16-CE29-0028)the National Natural Science Foundation of China (Nos. 21604001 and 21528402)
文摘Fluorescent vesicles have recently attracted increasing attention because of their potential applications in bioimaging,diagnostics, and theranostics, for example, in vivo study of the delivery and the distribution of active substances. However, fluorescent vesicles containing conventional organic dyes often suffer from the problem of aggregation-caused quenching(ACQ) of fluorescence.Fluorescent vesicles working with aggregation-induced emission(AIE) offer an extraordinary tool to tackle the ACQ issue, showing advantages such as high emission efficiency, superior photophysical stability, low background interference, and high sensitivity. AIE fluorescent vesicles represent a new type of fluorescent and functional nanomaterials. In this review, we summarize the recent advances in the development of AIE fluorescent vesicles. The review is organized according to the chemical structures and architectures of the amphiphilic molecules that constitute the AIE vesicles, i.e., small-molecule amphiphiles, amphiphilic polymers, and amphiphilic supramolecules and supramacromolecules. The studies on the applications of these AIE vesicles as stimuli-responsive vesicles,fluorescence-guided drug release carriers, cell imaging tools, and fluorescent materials based on fluorescence resonance energy transfer(FRET) are also discussed.
基金This work was supported by the Beijing Talent Fund for Young Sci-Tech Researchers (No. H013610050112)
文摘A new dinuclear centrosymmetric complex [LaL（HL）（H2O）3]2（2H2O （H2L = 3-nitrophthalic acid, NPA） was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The complex crystallizes in triclinic system, space group P1^- with a = 8.1549（16）, b = 8.8856（18）, c = 15.277（3）A,α= 100.93（3）,α= 90.81（3）, γ= 104.56（3）°, V = 1049.8（4）A^3, Z = 1,μ= 2.125 mm^-1, Dc=1.994 g/cm^3, R = 0.0259 and wR = 0.0679. Two 3-nitrophthalates（2-） coordinate with the La3＋ ions in a bridging mode, and two monohydrogen- 3-nitrophthates（1-） and three waters in terminal ways, respectively. Each La^3＋ ion is nine-coordinated to exhibit a distorted tricapped trigonal prism coordination polyhedron. Both the coordinated and crystal waters are involved in the inter- and intramolecular hydrogen bonds. The dinuclear units are linked into a 2D network structure in the ab plane via intermolecular hydrogen bonds along the axes a and b. Two crystal waters fill each rhombic pore of the network. The networks are further packed along the c axis forming a layered supramolecular structure through the C-H…O weak forces between the adjacent sheets. TGA analysis shows the complex undergoes the loss of waters of crystallization and coordination and the decomposition of ligands sequentially.
