Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, a...Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a = 9.487（3）,b = 20.674（6）, c = 11.821（4）A, β = 113.416（8）o, Mr = 825.06, V = 2127.5（12） A^3, Z = 2, Dc = 1.288g/cm^3, μ = 0.18 mm^-1, F（000） = 876, MoK α radiation（λ = 0.71073 A）, the final R = 0.0472 and wR = 0.0930. A total of 3758 unique reflections were collected, of which 3313 with I 〉 2σ（I） were observed. Compound 1-H2PO4^-crystallizes in triclinic, space group P21/n, with a = 8.767（1）, b =13.6190（15）, c = 16.615（2） ？, α = 98.727（14）, β = 103.061（14）, γ = 91.382（16）°, Mr = 1357.75, V =1906.6（4） A^3, Z = 1, Dc = 1.183 g/cm^3, μ = 0.17 mm-（-1）, F（000） = 734, MoK α radiation（λ = 0.71073？）, the final R = 0.0769 and wR = 0.1884. A total of 6699 unique reflections were collected, of which 2989 with I 〉 2σ（I） were observed. As it was observed in the crystal structure of 1-H2PO4^-, 1bound H2PO4^-at a 1：2 ratio by intermolecular interaction of N-H···O hydrogen bond obviously.Another interesting feature was that H2PO4--groups assembled chains themselves via intramolecular hydrogen bond O-H···O and connected the 1 molecules together through the interaction of H-bonds,which improved the planarity of 1 and increased the stability of the entire structure.展开更多
Three new suprarnolecular networks based on paratungstate and N-donor bridging ligands, [H2bpmp]2,5H[H2W12O40]·2H20（1）, [H2（bpp）]2[H（py-CH3）]0.25 [H（py-C2Hs）]0.25H1.5[H2W12O40]·4H2O（2） and [H2pip]3...Three new suprarnolecular networks based on paratungstate and N-donor bridging ligands, [H2bpmp]2,5H[H2W12O40]·2H20（1）, [H2（bpp）]2[H（py-CH3）]0.25 [H（py-C2Hs）]0.25H1.5[H2W12O40]·4H2O（2） and [H2pip]3[H2W12O40]（3）[bpmp=N,N＇-bis（4-pyridylmethyl）piperazine; bpp=l,3-bis（4-pyridyl）propane; py=pyridine; pip=piperazine] were prepared by the hydrothermal synthesis and characterized by elemental analysis, infrared（IR）, thermogravimetric（TG） analysis and single-crystal X-ray diffraction（XRD）. All the compounds show high-dimen- sional suprarnolecular networks based on [H2W12O40]^6- and the protonated N-donor ligands via the N-H.…O-W hydrogen bonds and/or π…πstacking interactions. Their luminescent properties were investigated.展开更多
The title complex, {[Cu2（4,4＇-bipyridine）2（μ-O2CMe）2（O2CMe）2],H2O}n 1, was synthesized and structurally characterized by X-ray crystallography. It crystallizes in monoclinic, space group C2/c with a = 13.4474...The title complex, {[Cu2（4,4＇-bipyridine）2（μ-O2CMe）2（O2CMe）2],H2O}n 1, was synthesized and structurally characterized by X-ray crystallography. It crystallizes in monoclinic, space group C2/c with a = 13.4474（5）, b = 11.7566（2）, c = 19.5380（6）A, β = 92.930（2）°, V = 3084.84（16） A^3, Z = 4, Cu2C28N409H30, Mr = 693.64, Dc = 1.494 g/cm^3, F（000） = 1424 and μ（MoKα） = 1.436 mm^-1. With the use of 2062 observed reflections （I 〉 2σ（I））, the structure was refined to R = 0.0769 and wR = 0.2154. In complex 1, the dimeric copper acetate units are linked through 4,4’-bipyridine to yield ID molecular ladders. These ladders are connected via O-H…O hydrogen bonds to generate 2D layers, which are further linked through C-H…O hydrogen bonds to give a 3D supramolecular network.展开更多
A new compound [Zn3（C7NO4H3）3Cl4]·[C6NO2H6]4·4H2O （I） has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018（14）,b=12...A new compound [Zn3（C7NO4H3）3Cl4]·[C6NO2H6]4·4H2O （I） has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018（14）,b=12.6902（10）,c=25.1170（2）,β=90.54°,V=5387.0（8）3,Z=4,Zn3C45H41Cl4N7O24,Mr=1401.76,Dc=1.728 g/cm3,F（000）=2840,μ（MoKa）=1.615 mm-1,the R= 0.0758 and wR=0.2060 for 3468 observed reflections （I 〉 2σ（I））.Analysis of single-crystal X-ray diffraction data shows that compound I displays an interesting example of 3D supramolecular networks with perfect neutral and ionic hydrogen bonding array.展开更多
Superwetting aerogel is a promising alternative for the remediation of emulsified oily wastewater for its high porosity combined with extreme wettability enabled high separation performances to emulsion wastewater. Ho...Superwetting aerogel is a promising alternative for the remediation of emulsified oily wastewater for its high porosity combined with extreme wettability enabled high separation performances to emulsion wastewater. However, it remains challenging for superwetting aerogels to accomplish high-performance dual separation to surfactantstabilized oil-in-water(O/W) and water-in-oil(W/O) emulsions with high stability. Herein, an environmentally benign superamphiphilic composite aerogel was prepared by a green synthesis route that relied on the utilization of natural amphiphilic biomass. Collagen fibers(CFs) were utilized to construct the three-dimensional(3D) supramolecular skeleton of aerogel to provide high storage capacity of water/oil and outstanding capillary effect to boost the mass transfer. The two-dimensional(2D) lamellar structure of gelatin(Gel) was further grown on the skeleton of CFs aerogel to play the role for simultaneously enhanced demulsifying capability and spreading of emulsions. The as-prepared superamphiphilic aerogel enabled the separation of highly stable surfactant-stabilized O/W and W/O emulsions with high separation efficiency and flux. Excellent recycling performances and anti-fouling performance were also confirmed. Our investigations therefore demonstrated that the structural engineering of superamphiphilic aerogel is a promising way to realize high-performance dual separation of surfactant-stabilized O/W and W/O emulsion wastewater.展开更多
In this review a series of organic-based open porous networks are discussed, in which hydrogen bonds play an important role in network formation. Using these open networks as molecular templates: 1) a wealth of functi...In this review a series of organic-based open porous networks are discussed, in which hydrogen bonds play an important role in network formation. Using these open networks as molecular templates: 1) a wealth of functional vip species can be immo- bilized; 2) fullerene molecules can be separated and recognized; 3) photoisomerization reactions can be observed by STM; 4) 1D molecular arrays can be constructed; and 5) heterogeneous bilayer structures can be formed. It is envisioned that these su- pramolecular networks might be developed into a new family of useful soft frameworks for studies toward shape-selective ca- talysis, molecular recognition and host-vip supramolecular chemistry.展开更多
Hydrogen bonding has been employed to suppressnonradiative decay in organic compounds that showroom-temperature phosphorescence (RTP);however, the small number of structurally diverse examplesmakes it unclear how gene...Hydrogen bonding has been employed to suppressnonradiative decay in organic compounds that showroom-temperature phosphorescence (RTP);however, the small number of structurally diverse examplesmakes it unclear how general this strategy is to turnon RTP. In this study, we report highly efficient blueRTP from 4,4′,4′′-nitrilotribenzoic acid (TPA-CO_(2)H)in five structurally and chemically distinct hydrogenbonded supramolecular networks. In doped films inpoly(vinyl alcohol) (PVA), the phosphorescencequantum yield and lifetime (ΦPh and τPh) reach 52%and 275 ms. Boric acid can also be used to turn onRTP, and the performance changes significantlywhen the sample is heated beyond the dehydrationtemperature of this host where there is a 14-foldenhancement in the ΦPh after heat treatment. BlueRTP similar to that observed in PVA was also observed using granulated sugar, gelatine, and paper ashost matrices. This work elucidates for the first timethe role and the generality of hydrogen bonding inactivating efficient blue RTP and examines how thechoice of hydrogen bonding host influences RTPperformance. We further demonstrate how the emission color can be tuned by codoping the films withRhodamine 6G.展开更多
A novel compound (NH4)2Y(H2O)8[PMo10V2O40]·10H2O has been prepared in an aqueous solution and characterized by elemental analysis, IR, and TG-DTG analysis. X-ray diffraction analysis was carried out on (NH4)2Y(H2...A novel compound (NH4)2Y(H2O)8[PMo10V2O40]·10H2O has been prepared in an aqueous solution and characterized by elemental analysis, IR, and TG-DTG analysis. X-ray diffraction analysis was carried out on (NH4)2Y(H2O)8 [PMo10V2O40]·10H2O single crystal, which crystallizes in the monoclinic system of a space group P21/C with a=0.9871(3) nm,b=1.5424(5) nm,c=2.7924(9) nm,β=94.183(5)°and Z=2. In the compound, a two-dimensional network is constructed by the PMo10V2O405- anion and the Y(H2O)83+ cation building blocks via hydrogen bonding exhibiting the porous structure.展开更多
A new coordination compound [Mg（L）（H2 O）5·H2 O]（NKU-109, H2 L=5-（4 H-1,2,4-triazol-4-yl）benzene-1,3-dicarboxylic acid） was solvothermally synthesized, featuring a supramolecular hydrogen-bonding network. ...A new coordination compound [Mg（L）（H2 O）5·H2 O]（NKU-109, H2 L=5-（4 H-1,2,4-triazol-4-yl）benzene-1,3-dicarboxylic acid） was solvothermally synthesized, featuring a supramolecular hydrogen-bonding network. A good proton conductivity of 5.87×10^-4S/cm was recorded at 70℃ and a relative humidity of75% in alternating current（AC） impedance experiment, which sheds a new light on the design of proton conduction materials based on coordination compounds.展开更多
A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during ...A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during fabricating the support.Using this strategy,supported CuBr/di-（2-picolyl） amine catalyst with U-shaped fibrillar network was prepared and used in atom transfer radical polymerization of methyl methacrylate.XPS and SEM characterization of the catalyst revealed homogeneous distribution of ligand,sufficient reactive sites,adequate mechanical strength and macroporosity.The polymerization results demonstrated high activity and reusability of such catalyst.This strategy might be extended to other supported catalysts used in column reactors.展开更多
Supramolecular polymer networks(SPNs)are celebrated for their dynamic nature,yet they often exhibit inadequate mechanical properties.Thus far,the quest to bolster the mechanical resilience of SPNs while preserving the...Supramolecular polymer networks(SPNs)are celebrated for their dynamic nature,yet they often exhibit inadequate mechanical properties.Thus far,the quest to bolster the mechanical resilience of SPNs while preserving their dynamic character presents a formidable challenge.Herein,we introduce[2]rotaxane into SPN to serve as another cross-link,which could effectively enhance the mechanical robustness of the polymer network without losing the dynamic properties.Compared with SPN,the dually cross-linked network(DPN)demonstrates superior breaking strength,Young’s modulus,puncture force and toughness,underscoring its superior robustness.Furthermore,the cyclic tensile tests reveal that the energy dissipation capacity of DPN rivals,and in some cases surpasses,that of SPN,owing to the efficient energy dissipation pathway facilitated by[2]rotaxane.In addition,benefiting from stable topological structure of[2]rotaxane,DPN exhibits accelerated recovery from deformation,indicating superior elasticity compared to SPN.This strategy elevates the performance of SPNs across multiple metrics,presenting a promising avenue for the development of high-performance dynamic materials.展开更多
A stimuli-responsive supramolecular polymer network has been constructed based on the host-vip interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction vip G2.The form...A stimuli-responsive supramolecular polymer network has been constructed based on the host-vip interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction vip G2.The formation mechanism of the supramolecular polymer network has been explored by the intensive study.With the addition of the competitive molecules and heating,the supramolecular polymer network could be dissociated and lead to clear changes in NMR spectroscopy and viscosity property.展开更多
A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and elec...A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146（6）, b=1.2581（8）, c=2.2316（14） nm, α=99.352（10）,β=97.209（9）, γ=103.935（9）°, V=2.422（3） nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F（000）=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections （I 〉 2σ（I））. In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.展开更多
The title compounds, [Co（H2O）6]（OVA）2·2H2O 1, [Ni（H2O）6]（OVA）2·2H2O 2 and [Zn（OVA）2·2H2O] 3 （HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate）, were synthesized and characterized by sing...The title compounds, [Co（H2O）6]（OVA）2·2H2O 1, [Ni（H2O）6]（OVA）2·2H2O 2 and [Zn（OVA）2·2H2O] 3 （HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate）, were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. Compounds 1 and 2 are both of triclinic with space group P1. The metal atom coordinated by six water molecules displays a slightly distorted octahedral configuration. Interestingly, the carboxyl group from HOVA ligand does not coordinate to the metal atom. Correspondingly, compound 3 belongs to the monoclinic system, space group C2/c. Each zinc（Ⅱ） atom exhibits a distorted four-coordinated tetrahedral geometry. Two monodentate carboxyl groups link one zinc（Ⅱ） atom to form a mononuclear molecule. The structure feature is different from that of compounds 1 and 2, which could be attributed to the different coordinated numbers and radii of Co（Ⅱ）, Ni（Ⅱ） and Zn（Ⅱ） atoms.展开更多
A new bis（imidazolium） compound,[H2L（H2btec）2]·H4btec（1,L=1,1＇-（butane-1,4-diyl）bis（imidazole）,H4btec=1,2,4,5-benzenetetracarboxylatic acid）,has been synthesized and structurally characterized by singl...A new bis（imidazolium） compound,[H2L（H2btec）2]·H4btec（1,L=1,1＇-（butane-1,4-diyl）bis（imidazole）,H4btec=1,2,4,5-benzenetetracarboxylatic acid）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The title compound crystallizes in the monoclinic system,space group Pnma,with a=13.3908（11）,b=13.9249（12）,c=16.2166（14）,V=2957.6（4）3,Z=4,Mr=698.55,Dc=1.569 mg/m3,F（000）=1448,μ（MoKα）=0.130 mm-1,the final R=0.0584 and wR=0.1538 for 4295 observed reflections with I2σ（I）.The compound consists of one 1,1＇-（butane-1,4-diyl）bis（imidazolium） cation,one neutral H4btec and one H2btec2-（Only two para carboxyl groups are deprotonated,and two protonated ones remain free） anion.A one-dimensional hydrogen bonding chain and a 2D hydrogen bonding network are formed via intermolecular N–H…O and O–H…O hydrogen bonds.These adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular network.展开更多
A new cobalt compound,{[Co（H2btec）（2,2＇-bipy）（H2O）3]·H2O}n （1,H4btec=1,2,4,5-benzenetetracarboxylic acid,2,2＇-bipy=2,2＇-bipyridine）,has been synthesized and charac-terized by single-crystal X-ray diffr...A new cobalt compound,{[Co（H2btec）（2,2＇-bipy）（H2O）3]·H2O}n （1,H4btec=1,2,4,5-benzenetetracarboxylic acid,2,2＇-bipy=2,2＇-bipyridine）,has been synthesized and charac-terized by single-crystal X-ray diffraction,elemental analysis,IR and X-ray powder diffraction.The crystal belongs to the triclinic system,space group P1,with a=7.230（3）,b=11.626（5）,c=14.001（6）,α=108.12（0）°,β=95.85（0）°,V=1095.33（157）3,C20H20CoN2O12,Mr=539.31,Z= 2,Dc=1.635 g/cm3,μ=0.855 mm-1,F（000）=554,R=0.0427 and wR=0.1042 for 3883 observed reflections （I 〉 2σ（I））.The title compound features a discrete molecular structure,which is connected with each other through extensive O-H…O hydrogen bonds into an intricate 3D supramolecular network.Additionally,two different patterns of π-π stacking interactions further consolidate the framework.展开更多
Supramolecular polymeric networks are viscoelastic materials characterized by time-dependent mechanical responses.We herein present a physicochemical strategy to investigate the molecular engineering mechanisms of the...Supramolecular polymeric networks are viscoelastic materials characterized by time-dependent mechanical responses.We herein present a physicochemical strategy to investigate the molecular engineering mechanisms of the entangled supramolecular polymeric networks with controlled crosslinks,enabling precise control of their viscoelastic and mechanical properties.The supramolecular crosslink comprises a cucurbit[7]uril(CB[7])host motif and a hexanoate-isoquinoline(HIQ)vip motif,which exhibits pH-dependent kinetics,with dissociation rate constant(k_(d))finely tuned over a broad range(10^(−5)to 1 s^(−1)).By in-situ modulation of the crosslink molecular property,we minimized perturbations to the network topology,thereby illuminating the roles of kd in dictating the viscoelasticity and mechanics of the entangled supramolecular polymeric networks.The linear viscoelasticity of the network scaled with the kd of CB[7]-HIQ crosslinks,while k_(d)also governed energy dissipation,selfrecovery,and rupture strain.Interestingly,the rupture stress of the networks was independent of kd.This research provides new insights into the molecular mechanism study of supramolecular polymeric networks and offers a pathway to finely control their macroscopic performance.展开更多
基金supported by the China Postdoctoral Science Foundation(No.2014M551053)Natural Science Foundation of Hebei Province(No.B2015203124)Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University
文摘Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a = 9.487（3）,b = 20.674（6）, c = 11.821（4）A, β = 113.416（8）o, Mr = 825.06, V = 2127.5（12） A^3, Z = 2, Dc = 1.288g/cm^3, μ = 0.18 mm^-1, F（000） = 876, MoK α radiation（λ = 0.71073 A）, the final R = 0.0472 and wR = 0.0930. A total of 3758 unique reflections were collected, of which 3313 with I 〉 2σ（I） were observed. Compound 1-H2PO4^-crystallizes in triclinic, space group P21/n, with a = 8.767（1）, b =13.6190（15）, c = 16.615（2） ？, α = 98.727（14）, β = 103.061（14）, γ = 91.382（16）°, Mr = 1357.75, V =1906.6（4） A^3, Z = 1, Dc = 1.183 g/cm^3, μ = 0.17 mm-（-1）, F（000） = 734, MoK α radiation（λ = 0.71073？）, the final R = 0.0769 and wR = 0.1884. A total of 6699 unique reflections were collected, of which 2989 with I 〉 2σ（I） were observed. As it was observed in the crystal structure of 1-H2PO4^-, 1bound H2PO4^-at a 1：2 ratio by intermolecular interaction of N-H···O hydrogen bond obviously.Another interesting feature was that H2PO4--groups assembled chains themselves via intramolecular hydrogen bond O-H···O and connected the 1 molecules together through the interaction of H-bonds,which improved the planarity of 1 and increased the stability of the entire structure.
基金Supported by the National Natural Science Foundation of China(No.91027002)the Fundamental Research Funds for the Central Universities,China(No.11CXPY002)
文摘Three new suprarnolecular networks based on paratungstate and N-donor bridging ligands, [H2bpmp]2,5H[H2W12O40]·2H20（1）, [H2（bpp）]2[H（py-CH3）]0.25 [H（py-C2Hs）]0.25H1.5[H2W12O40]·4H2O（2） and [H2pip]3[H2W12O40]（3）[bpmp=N,N＇-bis（4-pyridylmethyl）piperazine; bpp=l,3-bis（4-pyridyl）propane; py=pyridine; pip=piperazine] were prepared by the hydrothermal synthesis and characterized by elemental analysis, infrared（IR）, thermogravimetric（TG） analysis and single-crystal X-ray diffraction（XRD）. All the compounds show high-dimen- sional suprarnolecular networks based on [H2W12O40]^6- and the protonated N-donor ligands via the N-H.…O-W hydrogen bonds and/or π…πstacking interactions. Their luminescent properties were investigated.
基金This work was supported by the Science Foundation of Fujian Provincial Key Laboratory of Polymer Materials
文摘The title complex, {[Cu2（4,4＇-bipyridine）2（μ-O2CMe）2（O2CMe）2],H2O}n 1, was synthesized and structurally characterized by X-ray crystallography. It crystallizes in monoclinic, space group C2/c with a = 13.4474（5）, b = 11.7566（2）, c = 19.5380（6）A, β = 92.930（2）°, V = 3084.84（16） A^3, Z = 4, Cu2C28N409H30, Mr = 693.64, Dc = 1.494 g/cm^3, F（000） = 1424 and μ（MoKα） = 1.436 mm^-1. With the use of 2062 observed reflections （I 〉 2σ（I））, the structure was refined to R = 0.0769 and wR = 0.2154. In complex 1, the dimeric copper acetate units are linked through 4,4’-bipyridine to yield ID molecular ladders. These ladders are connected via O-H…O hydrogen bonds to generate 2D layers, which are further linked through C-H…O hydrogen bonds to give a 3D supramolecular network.
基金supported by the Natural Science Foundation of Fujian Province (2006F3042)
文摘A new compound [Zn3（C7NO4H3）3Cl4]·[C6NO2H6]4·4H2O （I） has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018（14）,b=12.6902（10）,c=25.1170（2）,β=90.54°,V=5387.0（8）3,Z=4,Zn3C45H41Cl4N7O24,Mr=1401.76,Dc=1.728 g/cm3,F（000）=2840,μ（MoKa）=1.615 mm-1,the R= 0.0758 and wR=0.2060 for 3468 observed reflections （I 〉 2σ（I））.Analysis of single-crystal X-ray diffraction data shows that compound I displays an interesting example of 3D supramolecular networks with perfect neutral and ionic hydrogen bonding array.
基金financially supported by the National Natural Science Foundation of China (No. 22178232)the Key Research and Development Program of Science and Technology Department of Sichuan Province (No. 2021ZYCD009)+1 种基金the National Key Research and Development Program (No. 2018YFC1901101)the Program of Sichuan University Featured Research Groups in Engineering Disciplines
文摘Superwetting aerogel is a promising alternative for the remediation of emulsified oily wastewater for its high porosity combined with extreme wettability enabled high separation performances to emulsion wastewater. However, it remains challenging for superwetting aerogels to accomplish high-performance dual separation to surfactantstabilized oil-in-water(O/W) and water-in-oil(W/O) emulsions with high stability. Herein, an environmentally benign superamphiphilic composite aerogel was prepared by a green synthesis route that relied on the utilization of natural amphiphilic biomass. Collagen fibers(CFs) were utilized to construct the three-dimensional(3D) supramolecular skeleton of aerogel to provide high storage capacity of water/oil and outstanding capillary effect to boost the mass transfer. The two-dimensional(2D) lamellar structure of gelatin(Gel) was further grown on the skeleton of CFs aerogel to play the role for simultaneously enhanced demulsifying capability and spreading of emulsions. The as-prepared superamphiphilic aerogel enabled the separation of highly stable surfactant-stabilized O/W and W/O emulsions with high separation efficiency and flux. Excellent recycling performances and anti-fouling performance were also confirmed. Our investigations therefore demonstrated that the structural engineering of superamphiphilic aerogel is a promising way to realize high-performance dual separation of surfactant-stabilized O/W and W/O emulsion wastewater.
文摘In this review a series of organic-based open porous networks are discussed, in which hydrogen bonds play an important role in network formation. Using these open networks as molecular templates: 1) a wealth of functional vip species can be immo- bilized; 2) fullerene molecules can be separated and recognized; 3) photoisomerization reactions can be observed by STM; 4) 1D molecular arrays can be constructed; and 5) heterogeneous bilayer structures can be formed. It is envisioned that these su- pramolecular networks might be developed into a new family of useful soft frameworks for studies toward shape-selective ca- talysis, molecular recognition and host-vip supramolecular chemistry.
基金S.W.thanks the China Scholarship Council(grant no.201906250199)for supportfunding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No.897098(AIERTP-PLED)+1 种基金support from the Marie Skłodowska-Curie Individual FellowshipWe also thank the United Kingdom’s Engineering and Physical Sciences Research Council for support(grant no.EP/W007517/1).
文摘Hydrogen bonding has been employed to suppressnonradiative decay in organic compounds that showroom-temperature phosphorescence (RTP);however, the small number of structurally diverse examplesmakes it unclear how general this strategy is to turnon RTP. In this study, we report highly efficient blueRTP from 4,4′,4′′-nitrilotribenzoic acid (TPA-CO_(2)H)in five structurally and chemically distinct hydrogenbonded supramolecular networks. In doped films inpoly(vinyl alcohol) (PVA), the phosphorescencequantum yield and lifetime (ΦPh and τPh) reach 52%and 275 ms. Boric acid can also be used to turn onRTP, and the performance changes significantlywhen the sample is heated beyond the dehydrationtemperature of this host where there is a 14-foldenhancement in the ΦPh after heat treatment. BlueRTP similar to that observed in PVA was also observed using granulated sugar, gelatine, and paper ashost matrices. This work elucidates for the first timethe role and the generality of hydrogen bonding inactivating efficient blue RTP and examines how thechoice of hydrogen bonding host influences RTPperformance. We further demonstrate how the emission color can be tuned by codoping the films withRhodamine 6G.
文摘A novel compound (NH4)2Y(H2O)8[PMo10V2O40]·10H2O has been prepared in an aqueous solution and characterized by elemental analysis, IR, and TG-DTG analysis. X-ray diffraction analysis was carried out on (NH4)2Y(H2O)8 [PMo10V2O40]·10H2O single crystal, which crystallizes in the monoclinic system of a space group P21/C with a=0.9871(3) nm,b=1.5424(5) nm,c=2.7924(9) nm,β=94.183(5)°and Z=2. In the compound, a two-dimensional network is constructed by the PMo10V2O405- anion and the Y(H2O)83+ cation building blocks via hydrogen bonding exhibiting the porous structure.
基金supported by the 973 Program of China (No. 2014CB845600)the National Natural Science Foundation of China (Nos. 21421001 and 21531005)the Natural Science Foundation of Tianjin(No. 15JCZDJC38800)
文摘A new coordination compound [Mg（L）（H2 O）5·H2 O]（NKU-109, H2 L=5-（4 H-1,2,4-triazol-4-yl）benzene-1,3-dicarboxylic acid） was solvothermally synthesized, featuring a supramolecular hydrogen-bonding network. A good proton conductivity of 5.87×10^-4S/cm was recorded at 70℃ and a relative humidity of75% in alternating current（AC） impedance experiment, which sheds a new light on the design of proton conduction materials based on coordination compounds.
基金support from the National Natural Science Foundation of China(Nos.20574041 and 20874055)Hi-tech Research and Development Program(863 plan) of China(No.2009AA062903)
文摘A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during fabricating the support.Using this strategy,supported CuBr/di-（2-picolyl） amine catalyst with U-shaped fibrillar network was prepared and used in atom transfer radical polymerization of methyl methacrylate.XPS and SEM characterization of the catalyst revealed homogeneous distribution of ligand,sufficient reactive sites,adequate mechanical strength and macroporosity.The polymerization results demonstrated high activity and reusability of such catalyst.This strategy might be extended to other supported catalysts used in column reactors.
基金support from the National Natural Science Foundation of China(Nos.22122105 and22071152)Natural Science Foundation of Shanghai(No.22dz1207603)+4 种基金the Shuguang Program of Shanghai Education Development Foundation and the Shanghai Municipal Education Commission(No.22SG11)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(No.SN-ZJU-SIAS-006)L.Y.acknowledges the financial support from the National Natural Science Foundation of China(No.22305150)Z.Z.acknowledges the financial support from the National Natural Science Foundation of China(Nos.22101175 and 52333001)supported by State Key Laboratory of Polyolefins and Catalysis and Shanghai Key Laboratory of Catalysis Technology for Polyolefins(No.SKL-LCTP-202301)。
文摘Supramolecular polymer networks(SPNs)are celebrated for their dynamic nature,yet they often exhibit inadequate mechanical properties.Thus far,the quest to bolster the mechanical resilience of SPNs while preserving their dynamic character presents a formidable challenge.Herein,we introduce[2]rotaxane into SPN to serve as another cross-link,which could effectively enhance the mechanical robustness of the polymer network without losing the dynamic properties.Compared with SPN,the dually cross-linked network(DPN)demonstrates superior breaking strength,Young’s modulus,puncture force and toughness,underscoring its superior robustness.Furthermore,the cyclic tensile tests reveal that the energy dissipation capacity of DPN rivals,and in some cases surpasses,that of SPN,owing to the efficient energy dissipation pathway facilitated by[2]rotaxane.In addition,benefiting from stable topological structure of[2]rotaxane,DPN exhibits accelerated recovery from deformation,indicating superior elasticity compared to SPN.This strategy elevates the performance of SPNs across multiple metrics,presenting a promising avenue for the development of high-performance dynamic materials.
基金supported by National Natural Science Foundation of China(Nos.21702153 and 21801194).
文摘A stimuli-responsive supramolecular polymer network has been constructed based on the host-vip interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction vip G2.The formation mechanism of the supramolecular polymer network has been explored by the intensive study.With the addition of the competitive molecules and heating,the supramolecular polymer network could be dissociated and lead to clear changes in NMR spectroscopy and viscosity property.
基金This work was supported by the National Natural Science Foundation of China (No. 20401008)
文摘A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146（6）, b=1.2581（8）, c=2.2316（14） nm, α=99.352（10）,β=97.209（9）, γ=103.935（9）°, V=2.422（3） nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F（000）=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections （I 〉 2σ（I））. In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.
基金supported by the National Natural Science Foundation of China (No. 20573073)the Natural Scientific Research Foundation of Shaanxi Provincial Education Office of China (No. 09JK826, 08JZ82 and 08JK490)
文摘The title compounds, [Co（H2O）6]（OVA）2·2H2O 1, [Ni（H2O）6]（OVA）2·2H2O 2 and [Zn（OVA）2·2H2O] 3 （HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate）, were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. Compounds 1 and 2 are both of triclinic with space group P1. The metal atom coordinated by six water molecules displays a slightly distorted octahedral configuration. Interestingly, the carboxyl group from HOVA ligand does not coordinate to the metal atom. Correspondingly, compound 3 belongs to the monoclinic system, space group C2/c. Each zinc（Ⅱ） atom exhibits a distorted four-coordinated tetrahedral geometry. Two monodentate carboxyl groups link one zinc（Ⅱ） atom to form a mononuclear molecule. The structure feature is different from that of compounds 1 and 2, which could be attributed to the different coordinated numbers and radii of Co（Ⅱ）, Ni（Ⅱ） and Zn（Ⅱ） atoms.
基金supported by the Natural Science Foundation of Henan Province (No 092102310075)
文摘A new bis（imidazolium） compound,[H2L（H2btec）2]·H4btec（1,L=1,1＇-（butane-1,4-diyl）bis（imidazole）,H4btec=1,2,4,5-benzenetetracarboxylatic acid）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The title compound crystallizes in the monoclinic system,space group Pnma,with a=13.3908（11）,b=13.9249（12）,c=16.2166（14）,V=2957.6（4）3,Z=4,Mr=698.55,Dc=1.569 mg/m3,F（000）=1448,μ（MoKα）=0.130 mm-1,the final R=0.0584 and wR=0.1538 for 4295 observed reflections with I2σ（I）.The compound consists of one 1,1＇-（butane-1,4-diyl）bis（imidazolium） cation,one neutral H4btec and one H2btec2-（Only two para carboxyl groups are deprotonated,and two protonated ones remain free） anion.A one-dimensional hydrogen bonding chain and a 2D hydrogen bonding network are formed via intermolecular N–H…O and O–H…O hydrogen bonds.These adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular network.
基金supported by 973 Program (2007CB815302,2009CB939803)Chinese Academy of Sciences (KJCX2.YW.319,KJCX2.YW.M10,KJCX2-YW-M05)the Knowledge Innovation Program of Chinese Academy of Science,and Fujian Key Laboratory of Nanomaterials (2006L2005)
文摘A new cobalt compound,{[Co（H2btec）（2,2＇-bipy）（H2O）3]·H2O}n （1,H4btec=1,2,4,5-benzenetetracarboxylic acid,2,2＇-bipy=2,2＇-bipyridine）,has been synthesized and charac-terized by single-crystal X-ray diffraction,elemental analysis,IR and X-ray powder diffraction.The crystal belongs to the triclinic system,space group P1,with a=7.230（3）,b=11.626（5）,c=14.001（6）,α=108.12（0）°,β=95.85（0）°,V=1095.33（157）3,C20H20CoN2O12,Mr=539.31,Z= 2,Dc=1.635 g/cm3,μ=0.855 mm-1,F（000）=554,R=0.0427 and wR=0.1042 for 3883 observed reflections （I 〉 2σ（I））.The title compound features a discrete molecular structure,which is connected with each other through extensive O-H…O hydrogen bonds into an intricate 3D supramolecular network.Additionally,two different patterns of π-π stacking interactions further consolidate the framework.
基金supported by the National Natural Science Foundation of China(grant no.22001149)Shandong Provincial Natural Science Foundation,China(grant no.ZR2020QB083)the Young Scholars Program of Shandong University,China,and the Fundamental Research Funds of Shandong University.
文摘Supramolecular polymeric networks are viscoelastic materials characterized by time-dependent mechanical responses.We herein present a physicochemical strategy to investigate the molecular engineering mechanisms of the entangled supramolecular polymeric networks with controlled crosslinks,enabling precise control of their viscoelastic and mechanical properties.The supramolecular crosslink comprises a cucurbit[7]uril(CB[7])host motif and a hexanoate-isoquinoline(HIQ)vip motif,which exhibits pH-dependent kinetics,with dissociation rate constant(k_(d))finely tuned over a broad range(10^(−5)to 1 s^(−1)).By in-situ modulation of the crosslink molecular property,we minimized perturbations to the network topology,thereby illuminating the roles of kd in dictating the viscoelasticity and mechanics of the entangled supramolecular polymeric networks.The linear viscoelasticity of the network scaled with the kd of CB[7]-HIQ crosslinks,while k_(d)also governed energy dissipation,selfrecovery,and rupture strain.Interestingly,the rupture stress of the networks was independent of kd.This research provides new insights into the molecular mechanism study of supramolecular polymeric networks and offers a pathway to finely control their macroscopic performance.
