Crystalline metal cluster-based organic-inorganic hybrid materials have emerged as a significant frontier in materials chemistry due to their unique structural designability and tunable properties.The bifunctional lig...Crystalline metal cluster-based organic-inorganic hybrid materials have emerged as a significant frontier in materials chemistry due to their unique structural designability and tunable properties.The bifunctional ligand 2-(hydroxymethyl)-2-(4-pyridyl)-1,3-propanediol(H3L),featuring both hard hydroxyl donors on one side and a soft pyridyl group on the other side,enables selective metal coordination via hard-soft acid-base(HSAB)theory and directs hierarchical metal cluster assembly.This review systematically summarizes the recent advances on metal cluster-based materials coordinated by H_(3)L,including their syntheses,crystal structures,and related physicochemical properties.展开更多
Surface active ionic liquids (SAILs) are considered as prominent materials in enhanced oil recovery thanks to their high interfacial activity. This study reports the preparation and applications of a nanostructure Tri...Surface active ionic liquids (SAILs) are considered as prominent materials in enhanced oil recovery thanks to their high interfacial activity. This study reports the preparation and applications of a nanostructure Tripodal imidazolium SAIL as an environmentally-friendly substitute to the conventional surfactants. The product has a star-like molecular structure centered by a triazine spacer, namely [(C_(4)im)_(3)TA][Cl_(3)], prepared by a one-step synthesis method and characterized with FT-IR, NMR, XRD, and SEM analysis methods. The interfacial tension of the system was decreased to about 78% at critical micelle concentration of less than 0.08 mol·dm^(−3). Increasing temperature, from 298.2 to 323.2 K, improved this capability. The solid surface wettability was changed from oil-wet to water-wet and 80% and 77% stable emulsions of crude oil–aqueous solutions were created after one day and one week, respectively. Compared to the Gemini kind homologous SAILs, the superior effects of the Tripodal SAIL were revealed and attributed to the strong hydrophobic branches in the molecule. The Frumkin adsorption isotherm precisely reproduced the generated IFT data, and accordingly, the adsorption and thermodynamic parameters were determined.展开更多
A new metal-organic coordination polymer {[Nd（tci）（H2O）2]·2H2O}n（1） has been synthesized based on the flexible tricarboxylate ligand tris（2-carboxyethyl）isocyanuric acid（H3tci） and structurally characte...A new metal-organic coordination polymer {[Nd（tci）（H2O）2]·2H2O}n（1） has been synthesized based on the flexible tricarboxylate ligand tris（2-carboxyethyl）isocyanuric acid（H3tci） and structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, infrared spectra（IR）, powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）. Complex 1 crystallizes in triclinic, space group P1 with a = 9.1648（11）, b = 9.3326（12）, c = 12.440（2） , C（12）H（20）N3O（13） Nd, Mr = 558.55, V = 886.9（2） 3, Z = 2, Dc = 2.092 g·cm-3, μ = 3.006 mm-1, F（000） = 554, 2.56〈θ〈25.00°, λ（Mo Kα） = 0.71073 , T = 293（2） K, the final R = 0.0662 and w R = 0.2071. X-ray diffraction analysis reveals that complex 1 is a two-dimensional layer, which is further assembled into a three-dimensional supramolecular architecture through hydrogen bonding interactions. The structure of complex 1 can be simplified as a rare 2-periodic uninodal {48·62} topology and a non-interpenetrating kgd topology. Furthermore, the thermal stability and photoluminescence property of 1 were investigated.展开更多
A novel tripodal receptor,1,3,5-tri((5,7-dimethyl-1,8-naphthyridin-2-yl-amino)methyl)-2,4,6-triethylbenzene(1) was synthesized from starting materials 2,6-diamino-pyridine(2) and 1,3,5-triethylbenzene(4) by three step...A novel tripodal receptor,1,3,5-tri((5,7-dimethyl-1,8-naphthyridin-2-yl-amino)methyl)-2,4,6-triethylbenzene(1) was synthesized from starting materials 2,6-diamino-pyridine(2) and 1,3,5-triethylbenzene(4) by three steps with an overall yield of 25%,and characterized by ESI-MS,FT-IR and ~1H NMR spectra.Additionally,its absorption and emission spectra were investigated.展开更多
A new tripodal ligand, N, N, N′, N′, N″, N″ hexaisopropyl 2, 2′, 2″ nitrilotris (2,1 ethoxy) triacetamide (L) and its new erbium picrate complex were prepared. The structure of the complex was determined by...A new tripodal ligand, N, N, N′, N′, N″, N″ hexaisopropyl 2, 2′, 2″ nitrilotris (2,1 ethoxy) triacetamide (L) and its new erbium picrate complex were prepared. The structure of the complex was determined by X ray crystal structure analysis. The result reveals that the Er 3+ is encapsulated by the three arms of the tripodal ligand, and nine coordinated by the bridged head nitrogen atom, all ether oxygen atoms and carbonyl oxygen atoms of the ligand, and two oxygen atoms of the bidentate picrate. The coordination polyhedron is a distorted mono-capped square antiprism.展开更多
Five complexes ([Cu(tpc)] 2+ 1, [Cu(tpa)] 2+ 2, [Co(tpa)] 2+ 3, [Fe(tpa)] 2+ 4 and [Mn(tpa)] 2+ 5) (tpc = N, N', N' tris[(2 pyridyl)methyl] 1,4,7 triaza cyclononane(L1) and tp...Five complexes ([Cu(tpc)] 2+ 1, [Cu(tpa)] 2+ 2, [Co(tpa)] 2+ 3, [Fe(tpa)] 2+ 4 and [Mn(tpa)] 2+ 5) (tpc = N, N', N' tris[(2 pyridyl)methyl] 1,4,7 triaza cyclononane(L1) and tpa = tris[2 ((2 pyridyl)methyl imino)ethyl]amine(L2)) were synthesized and characterized. The crystal structures of 1, 3 and 4 were determined by X ray crystallography. Electrochemical investigations over two cupric complexes reveal that 2 has a less negative redox potential than that of 1. Electronic spectra of 2, 3, 4 and 5 show that the distinction in metal ion results in a shift of the ligand based π*←π transition.展开更多
A new manganese compound [Mn8（tmp）2（Htmp）4（（CH3）3CCO2）4（py）2Cl2]·2py （1·2py, H3tmp = 1,1,1-tri（hydroxymethyl）propane, py = pyramid） has been synthesized and its structure was characterized by I...A new manganese compound [Mn8（tmp）2（Htmp）4（（CH3）3CCO2）4（py）2Cl2]·2py （1·2py, H3tmp = 1,1,1-tri（hydroxymethyl）propane, py = pyramid） has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. Compound 1 belongs to the triclinic system, space group P1 with a = 13.378（5）, b = 14.334（5）, c = 15.012（6） , α = 107.637（5）, β = 95.635（3）, γ = 92.825（4）°, V = 2720.7（17） 3, Z = 1, C76H124N4O26Cl2Mn8, Mr = 2022.23, Dc = 1.234 Mg/m3, μ = 1.007 mm-1, F（000） = 1052, T = 293（2） K, the final R = 0.0755 and wR = 0.2163 for all 6463 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the core of 1 contains a [Mn8] mixed-valence rod-like unit consisting of six edge-sharing triangles （Mn3）, each of which is bridged by a μ3-oxygen atom.展开更多
A pyridine-copper inclusion complex with [Cu(py)4Cl]+ core was prepared in the presence of tripodal ligand tbst {tbst = 1,3,5-tris(2-benzimidazol)sulfanylmethyl-2,4,6-trimethyl- benzene}, and its structure has been de...A pyridine-copper inclusion complex with [Cu(py)4Cl]+ core was prepared in the presence of tripodal ligand tbst {tbst = 1,3,5-tris(2-benzimidazol)sulfanylmethyl-2,4,6-trimethyl- benzene}, and its structure has been determined. It crystallizes in triclinic, space group P with a = 9.0822(2), b = 17.6026(4), c = 18.7156(4) ? a = 93.40, b = 91.2980(1), g = 91.5560(1), V = 2984.81(1) 3, C58H63Cl2CuN11O4S3, Mr = 1208.81, Z = 2, F(000) = 1262, Dc = 1.345 g/cm3, m = 0.615 mm-1, R = 0.0713 and wR = 0.1307 for 7798 observed reflections (I > 2s(I)). X-ray analysis reveals that the uncoordinated tbst and pyridine as vip molecules are included in the complex with formula {[Cu(py)4Cl]Cl}(tbst)(py)4H2O. The tbst, pyridine, aqua and Cl- anion in the com- plex form extensive hydrogen-bonding interactions, building up a quasi-dinuclear structure.展开更多
A new Mn（Ⅱ） coordination polymer {[Mn（timb）2（H2O）2]·（Cl）2·（H2O）2}n（1,timb = 1,3,5-tris-（imidazol-1-ylmethyl）benzene） has been synthesized and characterized by elemental analysis,IR,TG and sing...A new Mn（Ⅱ） coordination polymer {[Mn（timb）2（H2O）2]·（Cl）2·（H2O）2}n（1,timb = 1,3,5-tris-（imidazol-1-ylmethyl）benzene） has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774（13）,b=9.8720（15）,c=11.4898（16）A,α=93.378（3）,β= 95.471（3）,γ=101.101（3）°,V=1002.6（3）A^3,Mr=834.67,Dc=1.382 g/cm^3,μ（MoKα）=0.517mm^-1,F（000）=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I〉2σ（I）.It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.展开更多
A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystal...A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystallizes in orthorhombic, space group Pnma with a = 9.2515（19）, b = 12.729（3）, c = 17.273（4） A, V = 2034.0（7） A3, C16H20CoN13O, Mr = 469.38, Dc = 1.533 g/cm3, μ（MoKα） = 0.884 mm^-1, F（000） = 968, Z = 4, the final R = 0.0392 and wR = 0.0818 for 2430 observed reflections. In the complex, the amide ligand L acts as a tridentate fashion and coordinates to the Co（Ⅲ） ion through three nitrogen atoms, while the other three positions of the Co（Ⅲ） center are occupied by three terminal azide anions. The complex is connected as a 1D chain structure by intermolecular hydrogen bonds between the uncoordinated amide groups. In order to investigate the coordination ability, thermodynamic stability of the ligand L with the first-series transition metal ions （Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ） and Zn（Ⅱ）） has been studied by potentiometric titration, and the results show that the order of their stability constants conforms to the Irving-Williams sequence.展开更多
MnC_(24)H_(27)F_(12)N_7O_3P_2·C_2H_5OH, Mr-852, orthogonal, space group P21 3, a=15.220(2);Z=4; V=3525(1)~3; F(000)=1732; Dc=1.61g/cm^3; μ=5.52cm^(-1)(Mo Kα=0.71073). Manganese (Ⅱ) atom is seven-coordinated, w...MnC_(24)H_(27)F_(12)N_7O_3P_2·C_2H_5OH, Mr-852, orthogonal, space group P21 3, a=15.220(2);Z=4; V=3525(1)~3; F(000)=1732; Dc=1.61g/cm^3; μ=5.52cm^(-1)(Mo Kα=0.71073). Manganese (Ⅱ) atom is seven-coordinated, with the coordination polyhedron of a monocapped antitrigonal prism.展开更多
The Eu^(3+)and Gd^(3+)complexes with an N-(methylene-2-pyridine)-N,N-di(methylenephosphonate)ligand(H_(4)NP_(2py)),an analogue of nitrilotri(methylphosphonic)acid(H6NTP),were synthesized and structurally characterized...The Eu^(3+)and Gd^(3+)complexes with an N-(methylene-2-pyridine)-N,N-di(methylenephosphonate)ligand(H_(4)NP_(2py)),an analogue of nitrilotri(methylphosphonic)acid(H6NTP),were synthesized and structurally characterized by X-ray single crystal diffraction.The determined crystal structures([C(NH_(2))_(3)]_(5)[Ln(NP_(2py))_(2)]·12H_(2)O)are the first example of a monomeric Ln^(3+)complex encapsulated by two tripodal aminophosphonic ligands.Each of the NP_(2py) anions coordinates to Ln^(3+)through two oxygen atoms from each monodentate phosphonic group,amine nitrogen and pyridine nitrogen atoms,filling thus 8 coordination sites of Ln^(3+).The luminescence properties of[C(NH_(2))_(3)]_(5)[Eu(NP_(2py))_(2)]·12H_(2)O crystals were studied and compared with those of Eu-NP_(2py) complexes in solution.Speciation analysis of Ln-NP_(2py) complexes(Ln:NP_(2py)=1:2),performed by luminescence and potentiometric methods,showed that both[Ln(NP_(2py))]^(-)and[Ln(NP_(2py))_(2)]_(5-)species may exist in solution.However,the formation of the latter one occurs in alkaline solutions at pH as high as 8.By implementing the Specific Ion Interaction Theory(SIT)it was possible to calculate the thermodynamic stability constants of the[Eu(NP_(2py))]^(-)and[Eu(NP_(2py))_(2)]^(5-)complexes.The corresponding log β_(Eul)^(0) and log β_(EuL2)^(0) values are 16.3±0.11 and 19.5±0.15,respectively.展开更多
The separation of sulfate anions(SO_(4)2-)from water is a great challenge due to its high hydration energy.Using synthetic receptors that are designed with a size-complementary cavity for sulfate binding,sulfate anion...The separation of sulfate anions(SO_(4)2-)from water is a great challenge due to its high hydration energy.Using synthetic receptors that are designed with a size-complementary cavity for sulfate binding,sulfate anions could be extracted from water to the organic phase via liquid-liquid extraction(LLE)method.To understand the correlation between sulfate binding(recognition chemistry)and sulfate-separation efficiency across two phases,herein we prepared a family of tripodal hexaurea receptors bearing various terminal substitutions:4-nitrophenyl substituted L1,4-methylphenyl substituted L2,and hexyl-chain-substituted L_(3).The crystal structures of[L_(2)·SO_(4)]_(2)-and[L_(3)·SO_(4)]_(2)-and 1H NMR titrations suggested that the sulfate-binding affinity of these receptors were terminal substitution-dependent,where the H-bonding strength and secondary C-H⋯πinteractions were regulated.Comprehensive LLE studies indicated that all three receptors displayed highly efficient sulfate extraction with receptor-loading dependence and concentration independence.Relative sulfate-extraction efficiency was consistent with the sulfate-binding affinity of these receptors.Notably,using the hexyl-chain-substituted receptor L_(3),sulfate anions could be extracted and released by acidification for several cycles.Typical U-tube transport experiments demonstrated that over 70%of sulfate anions could be transported from the source phase to the receiving phase in 3 days across a bulk liquid membrane,which comprised the receptor L_(3).Our work shows a paradigm of how the sulfate-recognition property is correlated with sulfate separation via LLE,which may help to understand and promote the development of supramolecular recognition-based systems for achieving desired separations.展开更多
A new tripodal rhodamine B derivative 2 was designed and synthesized by tripodal trialdehyde and rhodamine B hydrazide for the first time.This derivative could be used as a fluorescent chemosensor for the selective an...A new tripodal rhodamine B derivative 2 was designed and synthesized by tripodal trialdehyde and rhodamine B hydrazide for the first time.This derivative could be used as a fluorescent chemosensor for the selective and sensitive determination of copper(II)in Tris-HCl buffer and ethanol aqueous mixed media.Under the optimum conditions described herein,fluorescence enhancement at 557/577 nm was linearly related to the concentration of copper(II)in the range of 0.10 to 10.00×10-5 mol·L-1,with a corre-lation coefficient of R2=0.9964(n=15)and a detection limit of 1.129×10-7 mol·L-1(the relative standard deviation for five repeated measurements at 4.00×10-5 mol·L-1 Cu(II)was 2.2%).The absorbance meas-urements at 557 nm were linearly related to the concentration of Cu(II)in the range of 0.50 to 25.00×10-5 mol·L-1,with a correlation coefficient of R2=0.9948(n=13)and a detection limit of 3.338×10-7mol·L-1.展开更多
Two new different Cu(Ⅱ) MOFs with the same 1,3,5-tris(1-imidazolyl) benzene(tib) ligand {[Cu(tib)2]·(H2O)2·Br2}n(1) and {[Cu2(tib)·Br·Cl]·2Br}n(2) were obtained by one pot synthesized of tib ...Two new different Cu(Ⅱ) MOFs with the same 1,3,5-tris(1-imidazolyl) benzene(tib) ligand {[Cu(tib)2]·(H2O)2·Br2}n(1) and {[Cu2(tib)·Br·Cl]·2Br}n(2) were obtained by one pot synthesized of tib with CuBr in the presences of HCl and water. X-ray single crystal diffraction analyses indicate that both complexes 1 and 2 have two dimensional frameworks containing different building blocks. Each Cu(Ⅱ) atom in complex 1 is coordinated by four N atoms from different tib ligands. However, there are two different cryptographic Cu(Ⅱ) atoms in complex 2, one is four coordinated by two bromine atoms and two N atoms from different tib ligands, the other is six coordinated by two chloride atoms and four N atoms from different tib ligands. The thermal gravimetric analysis of complexes 1 and 2 are depicted in the paper.展开更多
A new cadmium(Ⅱ) coordination polymer, [Cd(TITMB)_2]-(SO_4 )·21H_2O, whereTITMB = 1, 3, 5-tris (imidazol-1-yl-methyl) -2, 4, 6-trimethylbenzene, was obtained by self-assemblyof tripodal ligand TITMB with CdSO_4&...A new cadmium(Ⅱ) coordination polymer, [Cd(TITMB)_2]-(SO_4 )·21H_2O, whereTITMB = 1, 3, 5-tris (imidazol-1-yl-methyl) -2, 4, 6-trimethylbenzene, was obtained by self-assemblyof tripodal ligand TITMB with CdSO_4·2.7H_2O in acetonitrile, and characterized by X-raycrystallography. The crystal data belongs to monoclinic space group C_c with cell parameters a =1.16891(4) nm, b= 2.06671(6) nm, c = 2.48185(7) nm, β= 97.8560(10)°, R = 0.0487, wR =0.1211. Theresults of structure analysis indicate that each TITMB ligand coordinates three metal atoms and inturn each Cd(Ⅱ) atom with octahedral coordination geometry connects six nitrogen atoms of imidazolegroup from six different TITMB ligands to produce a 2D honeycomb network structure. There are a lotof water molecules linked by hydrogen bonds and occupied the channels formed intra- andinter-sheets.展开更多
A series of novel tripodal colorimetric anion sensors based on hydrazone CH=N--NH groups have been synthesized and their recognition behavior with anionic vips has been studied. In DMSO solutions, sensors 1 and 2 sh...A series of novel tripodal colorimetric anion sensors based on hydrazone CH=N--NH groups have been synthesized and their recognition behavior with anionic vips has been studied. In DMSO solutions, sensors 1 and 2 show colorimetric responses for F^-, H2PO4 and AcO^-, while in DMSO/H20 （9 ： 1, V/V） solutions, sensor 1 shows single selectivity for AcO^-. ^1H NMR titration confirms that the tripodal sensors could bind anions through the collaboration of three hydrazone groups and anions residing in the central cavity of the sensors.展开更多
Treatment of Ru(CO)(Cl)(H)(PPh3)3 with NaLOEt (LOEt-= [CpCo{P(O)(OEt)2}3]-) afforded the hydride complex (PPh3)(CO)-LOEtRu(H) (1), which has been characterized by X-ray crystallography. Similarly, the tricyclohexylpho...Treatment of Ru(CO)(Cl)(H)(PPh3)3 with NaLOEt (LOEt-= [CpCo{P(O)(OEt)2}3]-) afforded the hydride complex (PPh3)(CO)-LOEtRu(H) (1), which has been characterized by X-ray crystallography. Similarly, the tricyclohexylphosphine analogue, (PCy3)(CO)LOEtRu(H) (2), was synthesized from Ru(CO)Cl(H)(PCy3)2 and NaLOEt. Treatment of complex 1 with R'SO2N3 afforded the (arylsulfonyl)amido complexes LOEtRu(CO)(PPh3)(NHSO2R) (R = 2,4,6-i-Pr3C6H2 (3), 4-t-BuC6H4 (4)). The crystal structure of complex 3 has been determined. The Ru-N distance and Ru-N-S angle in 3 are 2.076(3) and 126.14(16)°, respectively. Reactions of complex 1 with acids have been studied.展开更多
A thiourea-based tripodal colorimetric anion sensor was synthesized.Its binding abilities with AcO—and halide anions in DM SO were studied by UV—Vis spectra.The sensor showed diferent color responses to these anions...A thiourea-based tripodal colorimetric anion sensor was synthesized.Its binding abilities with AcO—and halide anions in DM SO were studied by UV—Vis spectra.The sensor showed diferent color responses to these anions.Th e association constants an d diferent stoichiomelries were ded uced by nonlinear least—square curve fitting or linear fit—ting.展开更多
The tris（2-aminoethyl）amine （tren）-based tris（4-pyridylurea） receptor L has been synthesized and its anion binding properties were studied. The ligand forms a 2 ： 1 （host/vip） complex with MgSO4, [SO4^2 L2]...The tris（2-aminoethyl）amine （tren）-based tris（4-pyridylurea） receptor L has been synthesized and its anion binding properties were studied. The ligand forms a 2 ： 1 （host/vip） complex with MgSO4, [SO4^2 L2], in which a sulfate ion is encapsulated by six urea groups from the two ligands through multiple hydrogen bonds. The metal ions do not coordinate to the pyridyl groups but exist as the hydrate [Mg（H2O）6]2＋ and interact with the [SO4 L2] capsules in the outer coordination sphere to form a three dimensional extended structure. The anion binding behav- ior of ligand L in solution was studied.展开更多
文摘Crystalline metal cluster-based organic-inorganic hybrid materials have emerged as a significant frontier in materials chemistry due to their unique structural designability and tunable properties.The bifunctional ligand 2-(hydroxymethyl)-2-(4-pyridyl)-1,3-propanediol(H3L),featuring both hard hydroxyl donors on one side and a soft pyridyl group on the other side,enables selective metal coordination via hard-soft acid-base(HSAB)theory and directs hierarchical metal cluster assembly.This review systematically summarizes the recent advances on metal cluster-based materials coordinated by H_(3)L,including their syntheses,crystal structures,and related physicochemical properties.
基金The authors would like to acknowledge the Bu Ali Sina University and the Iran National Science Foundation:INSF,under Grant number of 99031559,for their financial supports.
文摘Surface active ionic liquids (SAILs) are considered as prominent materials in enhanced oil recovery thanks to their high interfacial activity. This study reports the preparation and applications of a nanostructure Tripodal imidazolium SAIL as an environmentally-friendly substitute to the conventional surfactants. The product has a star-like molecular structure centered by a triazine spacer, namely [(C_(4)im)_(3)TA][Cl_(3)], prepared by a one-step synthesis method and characterized with FT-IR, NMR, XRD, and SEM analysis methods. The interfacial tension of the system was decreased to about 78% at critical micelle concentration of less than 0.08 mol·dm^(−3). Increasing temperature, from 298.2 to 323.2 K, improved this capability. The solid surface wettability was changed from oil-wet to water-wet and 80% and 77% stable emulsions of crude oil–aqueous solutions were created after one day and one week, respectively. Compared to the Gemini kind homologous SAILs, the superior effects of the Tripodal SAIL were revealed and attributed to the strong hydrophobic branches in the molecule. The Frumkin adsorption isotherm precisely reproduced the generated IFT data, and accordingly, the adsorption and thermodynamic parameters were determined.
文摘A new metal-organic coordination polymer {[Nd（tci）（H2O）2]·2H2O}n（1） has been synthesized based on the flexible tricarboxylate ligand tris（2-carboxyethyl）isocyanuric acid（H3tci） and structurally characterized by single-crystal X-ray diffraction analyses, elemental analysis, infrared spectra（IR）, powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）. Complex 1 crystallizes in triclinic, space group P1 with a = 9.1648（11）, b = 9.3326（12）, c = 12.440（2） , C（12）H（20）N3O（13） Nd, Mr = 558.55, V = 886.9（2） 3, Z = 2, Dc = 2.092 g·cm-3, μ = 3.006 mm-1, F（000） = 554, 2.56〈θ〈25.00°, λ（Mo Kα） = 0.71073 , T = 293（2） K, the final R = 0.0662 and w R = 0.2071. X-ray diffraction analysis reveals that complex 1 is a two-dimensional layer, which is further assembled into a three-dimensional supramolecular architecture through hydrogen bonding interactions. The structure of complex 1 can be simplified as a rare 2-periodic uninodal {48·62} topology and a non-interpenetrating kgd topology. Furthermore, the thermal stability and photoluminescence property of 1 were investigated.
基金the National Natural Science Foundation of China(Nos.20671094 and 90610034)the foundation (No.GJHZ05) for Bureau of International Co-operation of Chinese Academy of Science.
文摘A novel tripodal receptor,1,3,5-tri((5,7-dimethyl-1,8-naphthyridin-2-yl-amino)methyl)-2,4,6-triethylbenzene(1) was synthesized from starting materials 2,6-diamino-pyridine(2) and 1,3,5-triethylbenzene(4) by three steps with an overall yield of 25%,and characterized by ESI-MS,FT-IR and ~1H NMR spectra.Additionally,its absorption and emission spectra were investigated.
文摘A new tripodal ligand, N, N, N′, N′, N″, N″ hexaisopropyl 2, 2′, 2″ nitrilotris (2,1 ethoxy) triacetamide (L) and its new erbium picrate complex were prepared. The structure of the complex was determined by X ray crystal structure analysis. The result reveals that the Er 3+ is encapsulated by the three arms of the tripodal ligand, and nine coordinated by the bridged head nitrogen atom, all ether oxygen atoms and carbonyl oxygen atoms of the ligand, and two oxygen atoms of the bidentate picrate. The coordination polyhedron is a distorted mono-capped square antiprism.
文摘Five complexes ([Cu(tpc)] 2+ 1, [Cu(tpa)] 2+ 2, [Co(tpa)] 2+ 3, [Fe(tpa)] 2+ 4 and [Mn(tpa)] 2+ 5) (tpc = N, N', N' tris[(2 pyridyl)methyl] 1,4,7 triaza cyclononane(L1) and tpa = tris[2 ((2 pyridyl)methyl imino)ethyl]amine(L2)) were synthesized and characterized. The crystal structures of 1, 3 and 4 were determined by X ray crystallography. Electrochemical investigations over two cupric complexes reveal that 2 has a less negative redox potential than that of 1. Electronic spectra of 2, 3, 4 and 5 show that the distinction in metal ion results in a shift of the ligand based π*←π transition.
基金Supported by the National Natural Science Foundation of China (Nos. 20633020 and 20973172)the National Basic Research Program of China (No. 2009CB220009)+1 种基金the Natural Science Foundation of Fujian Province (No. 2008J0175)the Fujian Province Youth Foundation (No. 2007F3112)
文摘A new manganese compound [Mn8（tmp）2（Htmp）4（（CH3）3CCO2）4（py）2Cl2]·2py （1·2py, H3tmp = 1,1,1-tri（hydroxymethyl）propane, py = pyramid） has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. Compound 1 belongs to the triclinic system, space group P1 with a = 13.378（5）, b = 14.334（5）, c = 15.012（6） , α = 107.637（5）, β = 95.635（3）, γ = 92.825（4）°, V = 2720.7（17） 3, Z = 1, C76H124N4O26Cl2Mn8, Mr = 2022.23, Dc = 1.234 Mg/m3, μ = 1.007 mm-1, F（000） = 1052, T = 293（2） K, the final R = 0.0755 and wR = 0.2163 for all 6463 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the core of 1 contains a [Mn8] mixed-valence rod-like unit consisting of six edge-sharing triangles （Mn3）, each of which is bridged by a μ3-oxygen atom.
基金This work was supported by the National Natural Science Foundation of China (No. 39970177 29733090 and 29973047)
文摘A pyridine-copper inclusion complex with [Cu(py)4Cl]+ core was prepared in the presence of tripodal ligand tbst {tbst = 1,3,5-tris(2-benzimidazol)sulfanylmethyl-2,4,6-trimethyl- benzene}, and its structure has been determined. It crystallizes in triclinic, space group P with a = 9.0822(2), b = 17.6026(4), c = 18.7156(4) ? a = 93.40, b = 91.2980(1), g = 91.5560(1), V = 2984.81(1) 3, C58H63Cl2CuN11O4S3, Mr = 1208.81, Z = 2, F(000) = 1262, Dc = 1.345 g/cm3, m = 0.615 mm-1, R = 0.0713 and wR = 0.1307 for 7798 observed reflections (I > 2s(I)). X-ray analysis reveals that the uncoordinated tbst and pyridine as vip molecules are included in the complex with formula {[Cu(py)4Cl]Cl}(tbst)(py)4H2O. The tbst, pyridine, aqua and Cl- anion in the com- plex form extensive hydrogen-bonding interactions, building up a quasi-dinuclear structure.
基金Supported by the National Basic Research Program of China (2006CB806104)Science Foundation for Youths of Guangxi Province (No 0991089)Initiation Found of Hechi University (No 2008QS-N022)
文摘A new Mn（Ⅱ） coordination polymer {[Mn（timb）2（H2O）2]·（Cl）2·（H2O）2}n（1,timb = 1,3,5-tris-（imidazol-1-ylmethyl）benzene） has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774（13）,b=9.8720（15）,c=11.4898（16）A,α=93.378（3）,β= 95.471（3）,γ=101.101（3）°,V=1002.6（3）A^3,Mr=834.67,Dc=1.382 g/cm^3,μ（MoKα）=0.517mm^-1,F（000）=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I〉2σ（I）.It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.
基金supported by the National Natural Science Foundation of China (No.20771083)
文摘A new Co（Ⅲ） complex with a tripodal amide ligand [CoL（N3）3] （L = N-acetyl- N＇,N＇-bis-[（2-pyridyl）methyl]-ethylenediamine） has been synthesized and characterized structurally by X-ray diffraction. It crystallizes in orthorhombic, space group Pnma with a = 9.2515（19）, b = 12.729（3）, c = 17.273（4） A, V = 2034.0（7） A3, C16H20CoN13O, Mr = 469.38, Dc = 1.533 g/cm3, μ（MoKα） = 0.884 mm^-1, F（000） = 968, Z = 4, the final R = 0.0392 and wR = 0.0818 for 2430 observed reflections. In the complex, the amide ligand L acts as a tridentate fashion and coordinates to the Co（Ⅲ） ion through three nitrogen atoms, while the other three positions of the Co（Ⅲ） center are occupied by three terminal azide anions. The complex is connected as a 1D chain structure by intermolecular hydrogen bonds between the uncoordinated amide groups. In order to investigate the coordination ability, thermodynamic stability of the ligand L with the first-series transition metal ions （Co（Ⅱ）, Ni（Ⅱ）, Cu（Ⅱ） and Zn（Ⅱ）） has been studied by potentiometric titration, and the results show that the order of their stability constants conforms to the Irving-Williams sequence.
文摘MnC_(24)H_(27)F_(12)N_7O_3P_2·C_2H_5OH, Mr-852, orthogonal, space group P21 3, a=15.220(2);Z=4; V=3525(1)~3; F(000)=1732; Dc=1.61g/cm^3; μ=5.52cm^(-1)(Mo Kα=0.71073). Manganese (Ⅱ) atom is seven-coordinated, with the coordination polyhedron of a monocapped antitrigonal prism.
文摘The Eu^(3+)and Gd^(3+)complexes with an N-(methylene-2-pyridine)-N,N-di(methylenephosphonate)ligand(H_(4)NP_(2py)),an analogue of nitrilotri(methylphosphonic)acid(H6NTP),were synthesized and structurally characterized by X-ray single crystal diffraction.The determined crystal structures([C(NH_(2))_(3)]_(5)[Ln(NP_(2py))_(2)]·12H_(2)O)are the first example of a monomeric Ln^(3+)complex encapsulated by two tripodal aminophosphonic ligands.Each of the NP_(2py) anions coordinates to Ln^(3+)through two oxygen atoms from each monodentate phosphonic group,amine nitrogen and pyridine nitrogen atoms,filling thus 8 coordination sites of Ln^(3+).The luminescence properties of[C(NH_(2))_(3)]_(5)[Eu(NP_(2py))_(2)]·12H_(2)O crystals were studied and compared with those of Eu-NP_(2py) complexes in solution.Speciation analysis of Ln-NP_(2py) complexes(Ln:NP_(2py)=1:2),performed by luminescence and potentiometric methods,showed that both[Ln(NP_(2py))]^(-)and[Ln(NP_(2py))_(2)]_(5-)species may exist in solution.However,the formation of the latter one occurs in alkaline solutions at pH as high as 8.By implementing the Specific Ion Interaction Theory(SIT)it was possible to calculate the thermodynamic stability constants of the[Eu(NP_(2py))]^(-)and[Eu(NP_(2py))_(2)]^(5-)complexes.The corresponding log β_(Eul)^(0) and log β_(EuL2)^(0) values are 16.3±0.11 and 19.5±0.15,respectively.
基金supported by the Beijing Natural Science Foundation(2222025)National Natural Science Foundation of China(91856102,21772154,22171023 and 22101024)W.Z.also acknowledgements the support of the Beijing Institute of Technology Research Fund Program for Young Scholars.We also thank support from Analysis&Testing Center of Beijing Institute of Technology for data collection.
文摘The separation of sulfate anions(SO_(4)2-)from water is a great challenge due to its high hydration energy.Using synthetic receptors that are designed with a size-complementary cavity for sulfate binding,sulfate anions could be extracted from water to the organic phase via liquid-liquid extraction(LLE)method.To understand the correlation between sulfate binding(recognition chemistry)and sulfate-separation efficiency across two phases,herein we prepared a family of tripodal hexaurea receptors bearing various terminal substitutions:4-nitrophenyl substituted L1,4-methylphenyl substituted L2,and hexyl-chain-substituted L_(3).The crystal structures of[L_(2)·SO_(4)]_(2)-and[L_(3)·SO_(4)]_(2)-and 1H NMR titrations suggested that the sulfate-binding affinity of these receptors were terminal substitution-dependent,where the H-bonding strength and secondary C-H⋯πinteractions were regulated.Comprehensive LLE studies indicated that all three receptors displayed highly efficient sulfate extraction with receptor-loading dependence and concentration independence.Relative sulfate-extraction efficiency was consistent with the sulfate-binding affinity of these receptors.Notably,using the hexyl-chain-substituted receptor L_(3),sulfate anions could be extracted and released by acidification for several cycles.Typical U-tube transport experiments demonstrated that over 70%of sulfate anions could be transported from the source phase to the receiving phase in 3 days across a bulk liquid membrane,which comprised the receptor L_(3).Our work shows a paradigm of how the sulfate-recognition property is correlated with sulfate separation via LLE,which may help to understand and promote the development of supramolecular recognition-based systems for achieving desired separations.
基金Supported by the Foundation of the Governor of Guizhou Province,China(Grant No.200617)the Talented Person Foundation of Guizhou University(Grant No.2007039)
文摘A new tripodal rhodamine B derivative 2 was designed and synthesized by tripodal trialdehyde and rhodamine B hydrazide for the first time.This derivative could be used as a fluorescent chemosensor for the selective and sensitive determination of copper(II)in Tris-HCl buffer and ethanol aqueous mixed media.Under the optimum conditions described herein,fluorescence enhancement at 557/577 nm was linearly related to the concentration of copper(II)in the range of 0.10 to 10.00×10-5 mol·L-1,with a corre-lation coefficient of R2=0.9964(n=15)and a detection limit of 1.129×10-7 mol·L-1(the relative standard deviation for five repeated measurements at 4.00×10-5 mol·L-1 Cu(II)was 2.2%).The absorbance meas-urements at 557 nm were linearly related to the concentration of Cu(II)in the range of 0.50 to 25.00×10-5 mol·L-1,with a correlation coefficient of R2=0.9948(n=13)and a detection limit of 3.338×10-7mol·L-1.
基金funded by the National Natural Science Foundation of China(21261009)Young Scientist Foundation of Jiangxi Provincethe Education Fund of Jiangxi Province(GJJ13434)
文摘Two new different Cu(Ⅱ) MOFs with the same 1,3,5-tris(1-imidazolyl) benzene(tib) ligand {[Cu(tib)2]·(H2O)2·Br2}n(1) and {[Cu2(tib)·Br·Cl]·2Br}n(2) were obtained by one pot synthesized of tib with CuBr in the presences of HCl and water. X-ray single crystal diffraction analyses indicate that both complexes 1 and 2 have two dimensional frameworks containing different building blocks. Each Cu(Ⅱ) atom in complex 1 is coordinated by four N atoms from different tib ligands. However, there are two different cryptographic Cu(Ⅱ) atoms in complex 2, one is four coordinated by two bromine atoms and two N atoms from different tib ligands, the other is six coordinated by two chloride atoms and four N atoms from different tib ligands. The thermal gravimetric analysis of complexes 1 and 2 are depicted in the paper.
文摘A new cadmium(Ⅱ) coordination polymer, [Cd(TITMB)_2]-(SO_4 )·21H_2O, whereTITMB = 1, 3, 5-tris (imidazol-1-yl-methyl) -2, 4, 6-trimethylbenzene, was obtained by self-assemblyof tripodal ligand TITMB with CdSO_4·2.7H_2O in acetonitrile, and characterized by X-raycrystallography. The crystal data belongs to monoclinic space group C_c with cell parameters a =1.16891(4) nm, b= 2.06671(6) nm, c = 2.48185(7) nm, β= 97.8560(10)°, R = 0.0487, wR =0.1211. Theresults of structure analysis indicate that each TITMB ligand coordinates three metal atoms and inturn each Cd(Ⅱ) atom with octahedral coordination geometry connects six nitrogen atoms of imidazolegroup from six different TITMB ligands to produce a 2D honeycomb network structure. There are a lotof water molecules linked by hydrogen bonds and occupied the channels formed intra- andinter-sheets.
基金Project supported by the National Natural Science Foundation of China （No. 20671077） and Natural Science Foundation of Gansu （No. 1010RT2A018）.
文摘A series of novel tripodal colorimetric anion sensors based on hydrazone CH=N--NH groups have been synthesized and their recognition behavior with anionic vips has been studied. In DMSO solutions, sensors 1 and 2 show colorimetric responses for F^-, H2PO4 and AcO^-, while in DMSO/H20 （9 ： 1, V/V） solutions, sensor 1 shows single selectivity for AcO^-. ^1H NMR titration confirms that the tripodal sensors could bind anions through the collaboration of three hydrazone groups and anions residing in the central cavity of the sensors.
基金supported by the Hong Kong Research Grants Council (602209)
文摘Treatment of Ru(CO)(Cl)(H)(PPh3)3 with NaLOEt (LOEt-= [CpCo{P(O)(OEt)2}3]-) afforded the hydride complex (PPh3)(CO)-LOEtRu(H) (1), which has been characterized by X-ray crystallography. Similarly, the tricyclohexylphosphine analogue, (PCy3)(CO)LOEtRu(H) (2), was synthesized from Ru(CO)Cl(H)(PCy3)2 and NaLOEt. Treatment of complex 1 with R'SO2N3 afforded the (arylsulfonyl)amido complexes LOEtRu(CO)(PPh3)(NHSO2R) (R = 2,4,6-i-Pr3C6H2 (3), 4-t-BuC6H4 (4)). The crystal structure of complex 3 has been determined. The Ru-N distance and Ru-N-S angle in 3 are 2.076(3) and 126.14(16)°, respectively. Reactions of complex 1 with acids have been studied.
基金supported by the National Natural Science Foundation of China(No.20372054).
文摘A thiourea-based tripodal colorimetric anion sensor was synthesized.Its binding abilities with AcO—and halide anions in DM SO were studied by UV—Vis spectra.The sensor showed diferent color responses to these anions.Th e association constants an d diferent stoichiomelries were ded uced by nonlinear least—square curve fitting or linear fit—ting.
基金the National Natural Science Foundation of China
文摘The tris（2-aminoethyl）amine （tren）-based tris（4-pyridylurea） receptor L has been synthesized and its anion binding properties were studied. The ligand forms a 2 ： 1 （host/vip） complex with MgSO4, [SO4^2 L2], in which a sulfate ion is encapsulated by six urea groups from the two ligands through multiple hydrogen bonds. The metal ions do not coordinate to the pyridyl groups but exist as the hydrate [Mg（H2O）6]2＋ and interact with the [SO4 L2] capsules in the outer coordination sphere to form a three dimensional extended structure. The anion binding behav- ior of ligand L in solution was studied.
