Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(...Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.展开更多
Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,...Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.展开更多
Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed...Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.展开更多
Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been construc...Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.展开更多
Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmeth...Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.展开更多
Based on the theory of crystallization,a solvent-free solid-liquid phase crystallization method called solid-melt crystallization was designed to prepare energetic coordination polymers.Two target compounds[Cu(NPyz)_(...Based on the theory of crystallization,a solvent-free solid-liquid phase crystallization method called solid-melt crystallization was designed to prepare energetic coordination polymers.Two target compounds[Cu(NPyz)_(4)NO_(3)]·NO_(3)(ECPs-1)and Cu(NPyz)_(4)(ClO_(4))_(2)(ECCs-2)were prepared through programmed heating and cooling by using 4-nitropyrazole(NPyz),(Cu(NO_(3))_(2)·5H_(2)O and Cu(ClO_(4))_(2)·5H_(2)O) as raw materials.In addition,crystallization pre-experiments and annealing experiments also verified the feasibility of the method.Their structures were confirmed by IR,elemental analysis,single-crystal X-ray diffraction and powder X-ray diffraction.The physicochemical properties and sensitivity test results showed that ECCs-2 has better thermal stability(T_(d)=221℃),while ECPs-1 is less sensitive to mechanical stimuli(IS=12 J,FS=240 N).Calculations based on EXPLO5 and the Kamlet-Jacobs equation showed that ECCs-2 has more considerable detonation performance(P=25.2 GPa,D=7.5 km/s).In comparison,the more intuitive results from the HN test,flame test,thermal resistance test and lead plate explosion test revealed that ECCs-2 has an“acceptable”detonation performance.The laser detonation test also showed that ECCs-2 is a promising excellent laser detonation material(E=408 mJ,P=24 W,τ=17 ms).展开更多
In this study,lipases of CALB(Candida antarctica lipase B),TLL(Thermomyces lanuginosa lipase),RML(Rhizomucor miehei lipase),CALA(Candida antarctica lipase A)and LU(Lecitase?Ultra)were encapsulated into the nucleotideh...In this study,lipases of CALB(Candida antarctica lipase B),TLL(Thermomyces lanuginosa lipase),RML(Rhizomucor miehei lipase),CALA(Candida antarctica lipase A)and LU(Lecitase?Ultra)were encapsulated into the nucleotidehybrid metal coordination polymers(CPs)for diacylglyerols(DAG)preparation.Guanosine 5'-monophosphate(GMP)and adenosine 5'-monophosphate(AMP)were used as coordinating molecules,and metal ions of Fe^(3+),Ba^(2+),Mn^(2+),Ni^(2+)and Cr^(3+)were applied to prepare matrix.Results indicated that,besides Ba^(2+)with AMP,all other metal ions can coordinate with AMP and GMP to generate CPs.In addition,the AMP/Ni was amorphous when standing temperature was 4℃,while it was crystalline when standing temperature was from 30 to 180℃.DAG content from 47.55%to 64.99%was obtained from glycerolysis by CALB@GMP/Ba,RML@GMP/Ba,TLL@GMP/Ba,RML@GMP/Mn and TLL@GMP/Mn.Additionally,CALB@GMP/Fe showed selectivity towards DAG formation in the esterification and DAG content up to 61.88%was obtained.展开更多
In this work, a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxyme...In this work, a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural(EMF) in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran(THF). The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H(100) at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers(PCPs) for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.展开更多
Two new coordination polymers,named {[Co3(pfca)6(phen)2]·2H2O}n(1) and[Cu(pfca)2(4,4'-bpy)(H2O)]n(2)(Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine),were hydrothermally synthesized an...Two new coordination polymers,named {[Co3(pfca)6(phen)2]·2H2O}n(1) and[Cu(pfca)2(4,4'-bpy)(H2O)]n(2)(Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine),were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis(TGA),and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P1 with a = 10.939(3),b = 12.430(4),c = 13.815(4) A,α=78.436(3),β= 70.261(3),γ= 80.268(3)°,V= 1721.8(9) A^3,Dc = 1.508 g/cm^3,Mr= 1564.06,Z = 1,F(000) = 799,μ= 0.802 mm^(-1),the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ(I).Complex 2 is of monoclinic system,space group P2/lc with a =15.4985(14),b = 15.8424(14),c = 10.9528(10) A,β= 107.1600(10)°,V= 2569.6(4) A^3,Dc = 1.468g/cm^3,Mr = 568.02,Z = 4,F(000) = 1164,μ= 0.906 mm^(-1),the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I〉 2σ(I).Complex 1 features linear Co(Ⅱ)-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu(Ⅱ)-chains that are further cohered together by extensive H-bonds.展开更多
The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges,...The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits: (1) nanoporous spin crossover materials with single metal nodes; (2) metal-radical approach with rigid organic radical ligands and single metal nodes; (C) PCPs with rigid organic ligands and metal oligomer nodes; (D) PCPs with metal complex linkers and polymetal cluster nodes; (E) PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious: the pore benefits from the big cluster according to "Scale Chemistry", and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.展开更多
Three lanthanide coordination polymers [Ln(bcpb)0.5(NO3)(DEF)2] (Ln = Y (1), Tb (2), Eu (3), H4bcpb = 2,5-bis(2,4-dicarboxyphenyl) pyridine and DEF = N,N-diethylformamide)) have been solvothermally sy...Three lanthanide coordination polymers [Ln(bcpb)0.5(NO3)(DEF)2] (Ln = Y (1), Tb (2), Eu (3), H4bcpb = 2,5-bis(2,4-dicarboxyphenyl) pyridine and DEF = N,N-diethylformamide)) have been solvothermally synthesized under hydrothermal conditions with a novel Hnbcpb ligand and trivalent lanthanide nitrates. Single-crystal X-ray diffraction analysis reveals that compounds 1-3 are isostructural and crystallize in the monoclinic system, space group P21/n. Crystal data for 1: C20H26N409Y, Mr = 555.36, a = 13.022(9), b = 17.778(12), c = 10.861(8) A, β= 100.208(3)°, V = 2475(3) A3, Z = 4; Crystal data for 2: C20H26N4OgTb, Mr = 625.37, a = 13.0476(4), b = 17.8037(7), c = 10.9398(3) A, β = 100.008(4)°, V = 2496.4(12) A3, Z = 4; Crystal data for 3: C20H26N409Eu, Mr = 618.41, a = 13.055(4), b = 17.833(5), c = 10.893(3)A, β = 100.133(4)°, V= 2496.4(12) A3, Z = 4. The compounds were characterized by thermogravimetric analysis (TGA), IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1-3 all feature 2D networks with -ABAB- fashions. The luminescent properties of compounds 1-3 and free H4bcpb ligand were investigated at room temperature. The results show that the H4bcpb ligand can efficiently transfer energy to the Tb(III) ions, while the energy is not fully transferred from the H4bcpb ligand to the Eu(III) ions.展开更多
The assembly reactions of o- (or m-, or p-) tetrafluorobenzenedicarboxylic acid (denoted as o-H2L, m-H2L and p-HzL, respectively), benzonitrile and Ag+ ion led to three compounds: [Ag2(PhCN)2(o-HL)2]n (1),...The assembly reactions of o- (or m-, or p-) tetrafluorobenzenedicarboxylic acid (denoted as o-H2L, m-H2L and p-HzL, respectively), benzonitrile and Ag+ ion led to three compounds: [Ag2(PhCN)2(o-HL)2]n (1), [Ag2(PhCN)2(m-HL)2]n (2) and [Ag2(PhCN)2(p-L)], (3). 1 and 2 feature a 1D coordination chain, while 3 bears a 2D net structure. A variety of weak interactions are observed in the compounds. Strong nwrinteractions connect the 1D chains into a 3D supramolecular network in 1. Hydrogen bonds connect the chains into layers in 2. Three types of interesting π-π interactions also assemble the 2D layers into a 3D overall structure in 3.展开更多
Reactions of CdX2(X=NO3-, ClO4-) with Hatza (atza=5-aminotetrazole-1-acetato anion) and 2,2′-bipyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in a methanol/aqueous solution produced a set of new Cd...Reactions of CdX2(X=NO3-, ClO4-) with Hatza (atza=5-aminotetrazole-1-acetato anion) and 2,2′-bipyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in a methanol/aqueous solution produced a set of new Cd(Ⅱ) coordination polymers, {[Cd(atza)(H2O)(2,2′-bipy)]ClO4}n (1), {[Cd(atza)(H2O)(1,10-phen)]ClO4 }n (2), {[Cd(atza)(H2O)(2,2′-bipy)]NO3}n (3) and {[Cd(atza)2 (1,10-phen)]·0.5H2O}n (4). Single-crystal X-ray diffraction analysis reveals that each Cd(Ⅱ) ion has a distorted octahedral coordination geometry in 1-4, and the Cd(Ⅱ) ion centers are connected through the tridentate atza bridging ligands to form a 2D layer (1-3) or ID chain (4) structure. The fluorescent properties of 2 and 4 are also discussed.展开更多
Two-dimensional coordination polymers(CPs) have aroused tremendous interest as electrocatalysts because the catalytic performance could be fine-tuned by their well-designed coordination layers with highly accessible a...Two-dimensional coordination polymers(CPs) have aroused tremendous interest as electrocatalysts because the catalytic performance could be fine-tuned by their well-designed coordination layers with highly accessible and active metal sites.However,it remains great challenge for CP-based catalysts to be utilized for electrocatalytic oxidation reactions due to their inefficient activities and low catalytic stabilities.Herein,we applied a mixed-metal strategy to fabricate two-dimensional Co_xNi_(1-x)-CPs with dual active sites for electrocatalytic water and urea oxidation.By metal ratio regulation in the twodimensional layer,an optimized Co_(2/3)Ni_(1/3)-CP exhibits a water oxidation performance with an overpotential of 325 mV at a current density of 10 mA cm^(-2) and a Tafel slope of 86 mV dec^(-1) in alkaline solution for oxygen evolution reaction.Importantly,a lower potential than that of commercial RuO_(2) is observed over20 mA cm^(-2).Co_(2/3)Ni_(1/3)-CP also displays a potential of 1.381 V at 10 mA cm^(-2) for urea oxidation reaction and a Tafel slope of 124 mV dec^(-1).This mixed-metal strategy to maximize synergistic effect of different metal centers may ultimately lead to promising electrocatalysts for small molecule oxidation reaction.展开更多
Two novel Ag coordination polymers based on tetrazole-yl acylamide, Ag(NTAA) (1, H-NTAA = N-(1H-tetrazol-5-yl)acetamide) and Ag(NTPA) (2, H-NTPA = N-(1H-tetrazol- 5-yl)propionamide) have been synthesized u...Two novel Ag coordination polymers based on tetrazole-yl acylamide, Ag(NTAA) (1, H-NTAA = N-(1H-tetrazol-5-yl)acetamide) and Ag(NTPA) (2, H-NTPA = N-(1H-tetrazol- 5-yl)propionamide) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction. Compound 1 features a 3-connected 4.82-fes network and compound 2 displays a ladder-like chain. The different structures between 1 and 2 are mainly related with the substituent groups oftetrazole-yl acylamide.展开更多
Three Zn^Ⅱ coordination polymers, [Zn(py)(H2O)(dpa)]n 1, [Zn2(4,4’-bipy)2(dpa)2]n 2 and [Zn(bpe)(H2O)2(Hdpa)2]n 3 (py=pyridine, H2dpa=diphenic acid, 4,4'-bipy-4,4'-bipyridine, bpe = 1,2-bis(4-pyr...Three Zn^Ⅱ coordination polymers, [Zn(py)(H2O)(dpa)]n 1, [Zn2(4,4’-bipy)2(dpa)2]n 2 and [Zn(bpe)(H2O)2(Hdpa)2]n 3 (py=pyridine, H2dpa=diphenic acid, 4,4'-bipy-4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane), were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in monoclinic, space group C2/c with a = 23.014(3), b = 8.7184(13), c = 18.091(3)A° ,8 = 95.964(3)°, V=3610.2(9)A°^3, Z=8, C19H15NO5Zn, Mr=402.69, Dc=1.482 g/cm^3, F(000)=1648, μ(MoKa)=1.389 mm^-1 the final R=0.0431 and wR = 0.1120 for 4239 observed reflections with 1〉2σ(I). 2 crystallizes in orthorhombic, space group Fddd with a=23.1613(5), b=24.0324(6), c=29.4785(1)A°, V= 16408.4(5) A°3, Z=32, C24H16N2O4Zn, Mr=461.76, Dc=1.495 g/cm^3, F(000)=7552, μ(MoKa)=1.232 mm^-1, the final R=0.0542 and wR=0.1724 for 3632 observed reflections with 1〉2σ(I). 3 crystallizes in orthorhombic, space group C2/c with a=19.142(4), b = 13.862(3), c = 15.625(3) A°,β=122.404(3)°, V= 3500.3(11)A°^3, Z=8, C2oHiTNO5Zn0.50, Mr=384.03, Dc=1.457 g/cm^3,F(000)=1592,μ(MoKα)=0.766 mm^-1, the final R=0.0400 and wR=0.1210 for 4024 observed reflections with I 〉 2σ(I).展开更多
A novel coordination polymer [(C8H20N)(Ag2I3)]n ([C8H20N]+ = tetraethyl ammo- nium (TEA)) was synthesized by the reaction of AgI and C8H20NI at room temperature with pH = 6.5, and structurally characterized by means o...A novel coordination polymer [(C8H20N)(Ag2I3)]n ([C8H20N]+ = tetraethyl ammo- nium (TEA)) was synthesized by the reaction of AgI and C8H20NI at room temperature with pH = 6.5, and structurally characterized by means of X-ray single-crystal diffraction. It crystallizes in orthorhombic, space group Pna21 with a = 7.3323(9), b = 18.250(2), c =12.5294(15) ?, C6.33H16.16NAg2I3, Mr = 702.76, V = 1676.6(4) ?3, Z = 4, Dc = 2.784 g/cm3, F(000) = 1256.6, μ(MoKα) = 7.828 mm-1, the final R = 0.0529 and wR = 0.1586 for 1189 observed reflections with I > 2σ(I). X-ray analysis shows that the [Ag2I3]n- chain is built up by AgI4 tetrahedron and in combination with quaternary ammonium cations ([C8H20N]+) by static attractive forces to form the so-called organic-inorganic hybrid material.展开更多
Photoacoustic(PA)imaging with much deeper tissue penetration and better spatial resolution had been widely employed for the prevention and diagnosis of many diseases.In this study,a new type of hydrogen peroxide(H_(2)...Photoacoustic(PA)imaging with much deeper tissue penetration and better spatial resolution had been widely employed for the prevention and diagnosis of many diseases.In this study,a new type of hydrogen peroxide(H_(2)O_(2)T-activated photoacoustic nanoprobe[Mn-AH nanoscale coordination polymer nanodots(NCPs)]was successfully synthesized by a simple one-step method in water phase containing 2,20-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)(ABTS),horse radish peroxidase(HRP),and manganese ion(Mn^(2+).After modification by polyethylene glycol(PEG),Mn-AH NCPs exhibited excellent stability and biocompatibility for in vivo H_(2)O_(2)-responsive chromogenic assay with great speci¯city and sensitivity.In the presence of H_(2)O_(2),colorless ABTS would be converted by HRP into the oxidized form with strong near-infrared(NIR)absorbance,enabling photoacoustic detection of endogenous H_(2)O_(2).Using H_(2)O_(2)-activated Mn-AH NCPs,we have successfully performed PA imaging and H_(2)O_(2)detection of subcutaneous murine colon CT26 tumor and deep-seated orthotopic bladder tumor.Due to the inherent Mn element existence inside the Mn-AH,this nanoprobe also serves as a good T1-weighted magnetic resonance imaging(MRI)contrast agent simultaneously.Lastly,after accomplishing its imaging functions,the Mn-AH NCPs could be cleared out from the body without any long-term toxicity,providing a new opportunity for cancer diagnosis and treatment.展开更多
Two new one-dimensional zigzag chain coordination polymers, [Co(hfipbb)(2,2'- bpy)(H2O)2]n 1 and [Co(hfipbb)(1,10-phen)(H2O)], 2, have been synthesized under hydrother- mal reactions from COCl2.6H20, 4,4...Two new one-dimensional zigzag chain coordination polymers, [Co(hfipbb)(2,2'- bpy)(H2O)2]n 1 and [Co(hfipbb)(1,10-phen)(H2O)], 2, have been synthesized under hydrother- mal reactions from COCl2.6H20, 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) and 2,2' -bipyridine or 1,10-phenanthroline ligands, respectively. Single-crystal X-ray analyses revealed that the zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O-H…O hydrogen-bonds and π…π stacking interactions. Crystal data for 1: CzTHajCoF6N2Os Mr = 641.38, orthorhombic, space group Pnna, a = 9.3820(19), b = 27.366(6), c = 10.106(2)A, V = 2594.8(9)A3, Z = 4, Dc = 1.642 g/cm3, F(000) = 1300,/t = 0.752 mm-l, R = 0.0311 and wR = 0.0924. Crystal data for 2: C29H18CoF6N2O5, Mr = 647.38, monoclinic, space group P21/n, a = 7.7626(16), b = 29.446(6), c = 11.281(2)A,β= 93.98(3)°, V= 2572.3(9)A3, Z = 4, Dc = 1.672 g/cm3, F(000) = 1308,μ= 0.757 mm-1, R = 0.0403 and wR = 0.0820.展开更多
Under hydrothermal conditions, the reactions of NiII/CuII ions with 3-(6-aminpyri- dinium-3-yl) benzoate (HL) afford two compounds [NiL2]n (1) and [CuL2(H2O)]n (2). On the basis of X-ray diffraction analysis...Under hydrothermal conditions, the reactions of NiII/CuII ions with 3-(6-aminpyri- dinium-3-yl) benzoate (HL) afford two compounds [NiL2]n (1) and [CuL2(H2O)]n (2). On the basis of X-ray diffraction analysis of the two compounds, the results show that compound 1 features one-dimensional (1D) double-strand coordination arrays, while 2 presents the 63-hcb layers. Both compounds are further constructed into a 3D supramolecular structure with the aid of weak secondary interactions. Thermal stabilities and magnetic properties of compounds 1 and 2 were also investigated.展开更多
文摘Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.
文摘Three coordination polymers[Mn(epda)(2,2'⁃bipy)(H_(2)O)](1),[Mn(epda)(phen)](2),and[Co_(2)(epda)2(bpe)2(H_(2)O)_(4)]·5H_(2)O(3)(H2epda=5⁃ethyl⁃pyridine⁃2,3⁃dicarboxylic acid,2,2'⁃bipy=2,2'⁃bipyridine,phen=phenanthroline,bpe=1,2⁃bis(4⁃pyridyl)ethylene)were synthesized by solvothermal reactions and characterized by single⁃crystal X⁃ray diffraction,thermogravimetric analyses,IR spectroscopy and elemental analysis.1 displays a 1D chain struc⁃ture,and these chains are joined by O-H…O hydrogen bonding andπ⁃πstacking interactions to generate a 2D layer structure.2 displays a 2D layer structure,and adjacent layers are generated 3D architecture throughπ⁃πstacking interactions.3 displays a 1D chain structure,and adjacent chains are generated double layer structure through O-H…O hydrogen bonding.The fluorescent properties of 1 and 3 indicate that they can potentially be used as a luminescent sensor.1 was highly selective and sensitive towards o⁃nitrophenol through different detection mechanisms,however,3 was highly selective and sensitive towards 2,4,6⁃trinitrophenol.In addition,the magnetic behavior of 2 has also been investigated.CCDC:2172533,1,2355773,2,2355774,3.
文摘Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.
文摘Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.
文摘Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.
基金the projects of National Natural Science Foundation of China(Grant Nos.22175025 and 21905023)for their generous financial support.
文摘Based on the theory of crystallization,a solvent-free solid-liquid phase crystallization method called solid-melt crystallization was designed to prepare energetic coordination polymers.Two target compounds[Cu(NPyz)_(4)NO_(3)]·NO_(3)(ECPs-1)and Cu(NPyz)_(4)(ClO_(4))_(2)(ECCs-2)were prepared through programmed heating and cooling by using 4-nitropyrazole(NPyz),(Cu(NO_(3))_(2)·5H_(2)O and Cu(ClO_(4))_(2)·5H_(2)O) as raw materials.In addition,crystallization pre-experiments and annealing experiments also verified the feasibility of the method.Their structures were confirmed by IR,elemental analysis,single-crystal X-ray diffraction and powder X-ray diffraction.The physicochemical properties and sensitivity test results showed that ECCs-2 has better thermal stability(T_(d)=221℃),while ECPs-1 is less sensitive to mechanical stimuli(IS=12 J,FS=240 N).Calculations based on EXPLO5 and the Kamlet-Jacobs equation showed that ECCs-2 has more considerable detonation performance(P=25.2 GPa,D=7.5 km/s).In comparison,the more intuitive results from the HN test,flame test,thermal resistance test and lead plate explosion test revealed that ECCs-2 has an“acceptable”detonation performance.The laser detonation test also showed that ECCs-2 is a promising excellent laser detonation material(E=408 mJ,P=24 W,τ=17 ms).
基金the National Natural Science Foundation of China(31772000)。
文摘In this study,lipases of CALB(Candida antarctica lipase B),TLL(Thermomyces lanuginosa lipase),RML(Rhizomucor miehei lipase),CALA(Candida antarctica lipase A)and LU(Lecitase?Ultra)were encapsulated into the nucleotidehybrid metal coordination polymers(CPs)for diacylglyerols(DAG)preparation.Guanosine 5'-monophosphate(GMP)and adenosine 5'-monophosphate(AMP)were used as coordinating molecules,and metal ions of Fe^(3+),Ba^(2+),Mn^(2+),Ni^(2+)and Cr^(3+)were applied to prepare matrix.Results indicated that,besides Ba^(2+)with AMP,all other metal ions can coordinate with AMP and GMP to generate CPs.In addition,the AMP/Ni was amorphous when standing temperature was 4℃,while it was crystalline when standing temperature was from 30 to 180℃.DAG content from 47.55%to 64.99%was obtained from glycerolysis by CALB@GMP/Ba,RML@GMP/Ba,TLL@GMP/Ba,RML@GMP/Mn and TLL@GMP/Mn.Additionally,CALB@GMP/Fe showed selectivity towards DAG formation in the esterification and DAG content up to 61.88%was obtained.
基金financially supported by the Natural Science Foundation of China(no.21576059)the Key Technologies R&D Program(no.2011BAE06B02)+1 种基金the International Science&Technology Cooperation Program of China(2010DFB60840)the Science and Technology Project of Guizhou Province(nos.[2012]6012 and[2011]3016)
文摘In this work, a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural(EMF) in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran(THF). The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H(100) at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers(PCPs) for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.
基金Supported by the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.14HASTIT017)the Program for Innovative Research Team(in Science and Technology)in University of Henan Province(No.14IRTSTHN008)+1 种基金the Foundation of Education Committee of Henan Province(No.142300410301)the National Natural Science Foundation of China(No.21571093)
文摘Two new coordination polymers,named {[Co3(pfca)6(phen)2]·2H2O}n(1) and[Cu(pfca)2(4,4'-bpy)(H2O)]n(2)(Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine),were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis(TGA),and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P1 with a = 10.939(3),b = 12.430(4),c = 13.815(4) A,α=78.436(3),β= 70.261(3),γ= 80.268(3)°,V= 1721.8(9) A^3,Dc = 1.508 g/cm^3,Mr= 1564.06,Z = 1,F(000) = 799,μ= 0.802 mm^(-1),the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ(I).Complex 2 is of monoclinic system,space group P2/lc with a =15.4985(14),b = 15.8424(14),c = 10.9528(10) A,β= 107.1600(10)°,V= 2569.6(4) A^3,Dc = 1.468g/cm^3,Mr = 568.02,Z = 4,F(000) = 1164,μ= 0.906 mm^(-1),the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I〉 2σ(I).Complex 1 features linear Co(Ⅱ)-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu(Ⅱ)-chains that are further cohered together by extensive H-bonds.
基金supported by the State Key Laboratory of Structural Chemistry, NNSFC (20733003)Chinese Academy of Sciences (KJCX2-YW-M05)+1 种基金973 Program (2007CB815301, 2006CB932900)the NSF of Fujian Province (2006L2005, 2006J0014)
文摘The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits: (1) nanoporous spin crossover materials with single metal nodes; (2) metal-radical approach with rigid organic radical ligands and single metal nodes; (C) PCPs with rigid organic ligands and metal oligomer nodes; (D) PCPs with metal complex linkers and polymetal cluster nodes; (E) PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious: the pore benefits from the big cluster according to "Scale Chemistry", and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.
基金supported by the Fundamental Research Funds for the Central Universities(JB-ZR1119)the Research Foundation for Talented Scholars(09BS518,13B0095)+1 种基金the NSF of Fujian Province(Nos.2013J01237)the Educational Office of Fujian Province(JA12010)
文摘Three lanthanide coordination polymers [Ln(bcpb)0.5(NO3)(DEF)2] (Ln = Y (1), Tb (2), Eu (3), H4bcpb = 2,5-bis(2,4-dicarboxyphenyl) pyridine and DEF = N,N-diethylformamide)) have been solvothermally synthesized under hydrothermal conditions with a novel Hnbcpb ligand and trivalent lanthanide nitrates. Single-crystal X-ray diffraction analysis reveals that compounds 1-3 are isostructural and crystallize in the monoclinic system, space group P21/n. Crystal data for 1: C20H26N409Y, Mr = 555.36, a = 13.022(9), b = 17.778(12), c = 10.861(8) A, β= 100.208(3)°, V = 2475(3) A3, Z = 4; Crystal data for 2: C20H26N4OgTb, Mr = 625.37, a = 13.0476(4), b = 17.8037(7), c = 10.9398(3) A, β = 100.008(4)°, V = 2496.4(12) A3, Z = 4; Crystal data for 3: C20H26N409Eu, Mr = 618.41, a = 13.055(4), b = 17.833(5), c = 10.893(3)A, β = 100.133(4)°, V= 2496.4(12) A3, Z = 4. The compounds were characterized by thermogravimetric analysis (TGA), IR spectroscopy, and X-ray single-crystal diffraction. Compounds 1-3 all feature 2D networks with -ABAB- fashions. The luminescent properties of compounds 1-3 and free H4bcpb ligand were investigated at room temperature. The results show that the H4bcpb ligand can efficiently transfer energy to the Tb(III) ions, while the energy is not fully transferred from the H4bcpb ligand to the Eu(III) ions.
基金Supported by the NNSFC (21071025,91122031, 21107008)Doctoral Fund of Ministry of Education of China (20100041120021)the Fundamental Research Funds for the Central Universities (DUT12YQ04)
文摘The assembly reactions of o- (or m-, or p-) tetrafluorobenzenedicarboxylic acid (denoted as o-H2L, m-H2L and p-HzL, respectively), benzonitrile and Ag+ ion led to three compounds: [Ag2(PhCN)2(o-HL)2]n (1), [Ag2(PhCN)2(m-HL)2]n (2) and [Ag2(PhCN)2(p-L)], (3). 1 and 2 feature a 1D coordination chain, while 3 bears a 2D net structure. A variety of weak interactions are observed in the compounds. Strong nwrinteractions connect the 1D chains into a 3D supramolecular network in 1. Hydrogen bonds connect the chains into layers in 2. Three types of interesting π-π interactions also assemble the 2D layers into a 3D overall structure in 3.
基金supported by the Foundation of Suzhou Science and Technology of Jiangsu Province(SYN201015)Key Laboratory of Advanced Functional Materials of Jiangsu Province of China (No.10KFJJ002)
文摘Reactions of CdX2(X=NO3-, ClO4-) with Hatza (atza=5-aminotetrazole-1-acetato anion) and 2,2′-bipyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in a methanol/aqueous solution produced a set of new Cd(Ⅱ) coordination polymers, {[Cd(atza)(H2O)(2,2′-bipy)]ClO4}n (1), {[Cd(atza)(H2O)(1,10-phen)]ClO4 }n (2), {[Cd(atza)(H2O)(2,2′-bipy)]NO3}n (3) and {[Cd(atza)2 (1,10-phen)]·0.5H2O}n (4). Single-crystal X-ray diffraction analysis reveals that each Cd(Ⅱ) ion has a distorted octahedral coordination geometry in 1-4, and the Cd(Ⅱ) ion centers are connected through the tridentate atza bridging ligands to form a 2D layer (1-3) or ID chain (4) structure. The fluorescent properties of 2 and 4 are also discussed.
基金supported by the National Natural Science Foundation of China (Grant number 21622105 and 21931004)the Natural Science Foundation of Tianjin (Grant number 18JCJQJC47200)+2 种基金the Fundamental Research Funds for the Central UniversitiesNankai University (63201016 and 63201043)the Ministry of Education of China (Grant number B12015)。
文摘Two-dimensional coordination polymers(CPs) have aroused tremendous interest as electrocatalysts because the catalytic performance could be fine-tuned by their well-designed coordination layers with highly accessible and active metal sites.However,it remains great challenge for CP-based catalysts to be utilized for electrocatalytic oxidation reactions due to their inefficient activities and low catalytic stabilities.Herein,we applied a mixed-metal strategy to fabricate two-dimensional Co_xNi_(1-x)-CPs with dual active sites for electrocatalytic water and urea oxidation.By metal ratio regulation in the twodimensional layer,an optimized Co_(2/3)Ni_(1/3)-CP exhibits a water oxidation performance with an overpotential of 325 mV at a current density of 10 mA cm^(-2) and a Tafel slope of 86 mV dec^(-1) in alkaline solution for oxygen evolution reaction.Importantly,a lower potential than that of commercial RuO_(2) is observed over20 mA cm^(-2).Co_(2/3)Ni_(1/3)-CP also displays a potential of 1.381 V at 10 mA cm^(-2) for urea oxidation reaction and a Tafel slope of 124 mV dec^(-1).This mixed-metal strategy to maximize synergistic effect of different metal centers may ultimately lead to promising electrocatalysts for small molecule oxidation reaction.
文摘Two novel Ag coordination polymers based on tetrazole-yl acylamide, Ag(NTAA) (1, H-NTAA = N-(1H-tetrazol-5-yl)acetamide) and Ag(NTPA) (2, H-NTPA = N-(1H-tetrazol- 5-yl)propionamide) have been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction. Compound 1 features a 3-connected 4.82-fes network and compound 2 displays a ladder-like chain. The different structures between 1 and 2 are mainly related with the substituent groups oftetrazole-yl acylamide.
文摘Three Zn^Ⅱ coordination polymers, [Zn(py)(H2O)(dpa)]n 1, [Zn2(4,4’-bipy)2(dpa)2]n 2 and [Zn(bpe)(H2O)2(Hdpa)2]n 3 (py=pyridine, H2dpa=diphenic acid, 4,4'-bipy-4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane), were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in monoclinic, space group C2/c with a = 23.014(3), b = 8.7184(13), c = 18.091(3)A° ,8 = 95.964(3)°, V=3610.2(9)A°^3, Z=8, C19H15NO5Zn, Mr=402.69, Dc=1.482 g/cm^3, F(000)=1648, μ(MoKa)=1.389 mm^-1 the final R=0.0431 and wR = 0.1120 for 4239 observed reflections with 1〉2σ(I). 2 crystallizes in orthorhombic, space group Fddd with a=23.1613(5), b=24.0324(6), c=29.4785(1)A°, V= 16408.4(5) A°3, Z=32, C24H16N2O4Zn, Mr=461.76, Dc=1.495 g/cm^3, F(000)=7552, μ(MoKa)=1.232 mm^-1, the final R=0.0542 and wR=0.1724 for 3632 observed reflections with 1〉2σ(I). 3 crystallizes in orthorhombic, space group C2/c with a=19.142(4), b = 13.862(3), c = 15.625(3) A°,β=122.404(3)°, V= 3500.3(11)A°^3, Z=8, C2oHiTNO5Zn0.50, Mr=384.03, Dc=1.457 g/cm^3,F(000)=1592,μ(MoKα)=0.766 mm^-1, the final R=0.0400 and wR=0.1210 for 4024 observed reflections with I 〉 2σ(I).
基金This work was supported by the Foundation of Education Committee of Fujian Province (JB03053, JB04016)
文摘A novel coordination polymer [(C8H20N)(Ag2I3)]n ([C8H20N]+ = tetraethyl ammo- nium (TEA)) was synthesized by the reaction of AgI and C8H20NI at room temperature with pH = 6.5, and structurally characterized by means of X-ray single-crystal diffraction. It crystallizes in orthorhombic, space group Pna21 with a = 7.3323(9), b = 18.250(2), c =12.5294(15) ?, C6.33H16.16NAg2I3, Mr = 702.76, V = 1676.6(4) ?3, Z = 4, Dc = 2.784 g/cm3, F(000) = 1256.6, μ(MoKα) = 7.828 mm-1, the final R = 0.0529 and wR = 0.1586 for 1189 observed reflections with I > 2σ(I). X-ray analysis shows that the [Ag2I3]n- chain is built up by AgI4 tetrahedron and in combination with quaternary ammonium cations ([C8H20N]+) by static attractive forces to form the so-called organic-inorganic hybrid material.
基金supported by the Innovation Fund of WNLO 2018WNLOKF024,the National Natural Science Foundation of China(U20A20254,52072253)the China Postdoctoral Science Foundation(2021TQ0229,2021M702381)Collaborative Innovation Center of Suzhou Nano Science and Technology,the 111 Project,Jiangsu Natural Science Fund for Distinguished Young Scholars(BK20211544)。
文摘Photoacoustic(PA)imaging with much deeper tissue penetration and better spatial resolution had been widely employed for the prevention and diagnosis of many diseases.In this study,a new type of hydrogen peroxide(H_(2)O_(2)T-activated photoacoustic nanoprobe[Mn-AH nanoscale coordination polymer nanodots(NCPs)]was successfully synthesized by a simple one-step method in water phase containing 2,20-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)(ABTS),horse radish peroxidase(HRP),and manganese ion(Mn^(2+).After modification by polyethylene glycol(PEG),Mn-AH NCPs exhibited excellent stability and biocompatibility for in vivo H_(2)O_(2)-responsive chromogenic assay with great speci¯city and sensitivity.In the presence of H_(2)O_(2),colorless ABTS would be converted by HRP into the oxidized form with strong near-infrared(NIR)absorbance,enabling photoacoustic detection of endogenous H_(2)O_(2).Using H_(2)O_(2)-activated Mn-AH NCPs,we have successfully performed PA imaging and H_(2)O_(2)detection of subcutaneous murine colon CT26 tumor and deep-seated orthotopic bladder tumor.Due to the inherent Mn element existence inside the Mn-AH,this nanoprobe also serves as a good T1-weighted magnetic resonance imaging(MRI)contrast agent simultaneously.Lastly,after accomplishing its imaging functions,the Mn-AH NCPs could be cleared out from the body without any long-term toxicity,providing a new opportunity for cancer diagnosis and treatment.
基金Supported by the NNSFC (20701022)the K. C. Wong Magna Fund in Ningbo University
文摘Two new one-dimensional zigzag chain coordination polymers, [Co(hfipbb)(2,2'- bpy)(H2O)2]n 1 and [Co(hfipbb)(1,10-phen)(H2O)], 2, have been synthesized under hydrother- mal reactions from COCl2.6H20, 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) and 2,2' -bipyridine or 1,10-phenanthroline ligands, respectively. Single-crystal X-ray analyses revealed that the zigzag chains of 1 and 2 are linked into three-dimensional supramolecular networks by both O-H…O hydrogen-bonds and π…π stacking interactions. Crystal data for 1: CzTHajCoF6N2Os Mr = 641.38, orthorhombic, space group Pnna, a = 9.3820(19), b = 27.366(6), c = 10.106(2)A, V = 2594.8(9)A3, Z = 4, Dc = 1.642 g/cm3, F(000) = 1300,/t = 0.752 mm-l, R = 0.0311 and wR = 0.0924. Crystal data for 2: C29H18CoF6N2O5, Mr = 647.38, monoclinic, space group P21/n, a = 7.7626(16), b = 29.446(6), c = 11.281(2)A,β= 93.98(3)°, V= 2572.3(9)A3, Z = 4, Dc = 1.672 g/cm3, F(000) = 1308,μ= 0.757 mm-1, R = 0.0403 and wR = 0.0820.
基金supported by the National Natural Science Foundation of China(Nos.21671119,21301106 and 21673127)
文摘Under hydrothermal conditions, the reactions of NiII/CuII ions with 3-(6-aminpyri- dinium-3-yl) benzoate (HL) afford two compounds [NiL2]n (1) and [CuL2(H2O)]n (2). On the basis of X-ray diffraction analysis of the two compounds, the results show that compound 1 features one-dimensional (1D) double-strand coordination arrays, while 2 presents the 63-hcb layers. Both compounds are further constructed into a 3D supramolecular structure with the aid of weak secondary interactions. Thermal stabilities and magnetic properties of compounds 1 and 2 were also investigated.