The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsa...The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.展开更多
The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1....The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.展开更多
The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1....The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.展开更多
The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2...The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2·2H2O with 2-amino-1,3-thiazole in methanol and characterized by IR spectra and X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=9.7137（2）,b=10.7005（2）,c=14.6505（2）,α=83.9550（10）,β=82.0930（10）,γ=67.1640（10）°,V=1387.84（4）3,Mr=883.43,Z=2,μ=3.927 mm-1,Dc=2.1144 g/cm3,F（000）=868,R=0.0332 and wR=0.0814.The complex contains a tetrahedron of four CuII atoms coordinating to a central μ4-O atom,with the six edges of the tetrahedron bridged by six Cl atoms.The Cu-O bond distances range from 1.910（2） to 1.918（2）,Cu-Cl from 2.3501（11） to 2.5924（10）,and Cu-Cu from 3.1003（6） to 3.1663（6）.The coordination geometries of the four coppers distort from trigonal bipramid to tetragonal pyramid with different distortion factors.The free animo groups of the ligands result in a lot of N-H···Cl and N-H···N intra-and intermolecular hydrogen bonds.展开更多
The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur...The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.展开更多
A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by e...A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal gravimetry （TG）, fluorescent emission and single-crystal X-ray diffraction. Its crystal structure is of monoclinic, space group P2 1/c with a = 9.8897（8）, b = 14.2506（12）, c = 26.384（2） ,A, β = 94.8940（10）°, V = 3704.8（5） A3 Z = 2, C86H52N16O16S2Zn4, Mr = 1891.04, Dc = 1.695 g/cm^3, μ= 1.423 mm^-1, F（000） = 1920, GOOF = 1.039, the final R = 0.0358 and wR = 0.0872 for 6038 observed reflections with I 〉 2σ（I）. In 1, ＂cage-like＂ tetranuclear clusters of [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] are further stacked through π-π interactions to generate a 3D supramolecular network.展开更多
The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central ...The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central μ_4-O atom and the four Nd atoms.The results of calculation show that the μ_4-O atom uses its sp^3 valence orbitals to contribute four O-Nd bonding MOs with character of multicenter bond apparent- ly.The Mulliken population analysis shows that the overlap population between Nd atoms is almost equal to zero,therefore there is no direct metal-metal bond between Nd atoms.The coordination number of Nd in the complex is discussed briefly.展开更多
The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by tipyridine-mediated conversion o...The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by tipyridine-mediated conversion of trinuclear [CrnFe3-nO(O2CMe)6(H2O)3]+(1, n=0; 2, n=1;3, n=3), and crystallized as three of approximate isomorphs. Crystal 2 is monoclinic with space group C2/c, a=27.454(5)A, b=11.789(1)A, c=16.570(3)A, B=118.78(1), V=4700.8A, z=4, u(MoKa)=11.64cm-1, F(000)=2056, final R=0.058 and Rw=0.066 for 3479 reflections with I > 3o(I). The Fe and Cr atoms in the cation are all +3 oxide state and disordered in the lattice, which is also supported by its Mossbauer studies. The [Cr2Fe2O2]8+ core can be thought of as being derived from two edge-sharing M3O units (M=Fe or Cr), and as a butterfly-like structure. The cations' structure of all three crystals are similar to each other and have C2 symmetry. The species are characterized by IR spectra and magnetic techniques, with particular emphasis on differentiation of coordination bond strengths and electronic environment of metal atoms in these complexes.展开更多
A new tetranuclear silver（I） complex with the formula of [Ag4（MMPzA）2（dmPz）4（H2DPC）2]（H2O）4（1, MMPz A = mono（3,5-bimethyl-pyrazolmethyl）amine）, dm Pz = 3,5-dimethylpyrazole, H2DPC = pyridine-3,4-dicarbox...A new tetranuclear silver（I） complex with the formula of [Ag4（MMPzA）2（dmPz）4（H2DPC）2]（H2O）4（1, MMPz A = mono（3,5-bimethyl-pyrazolmethyl）amine）, dm Pz = 3,5-dimethylpyrazole, H2DPC = pyridine-3,4-dicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction method. The title complex crystallizes in the triclinic system, space group P1 with a = 10.5532（13）, b = 11.5071（18）, c = 13.3951（17） A, α = 97.3190（10）, β = 106.7360（10）, γ = 108.0770（10）o, V = 1438.3（3） A3, Z = 1, Dc = 1.691 g/cm3, F（000） = 736, μ = 1.421 mm-1, the final R = 0.0400 and w R = 0.0942 for 5097 observed reflections（I 〉 2σ（I））. The intermolecular hydrogen bonding interaction extends the complex into a 1D chain structure. In addition, the complex was tested in vitro for its antibacterial activity and it exhibited significant activity, especially against penicillium.展开更多
In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip ...In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine), are synthesized from the reaction of well characterized Lewis base [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>O<sub>2</sub>] with carbon dioxide as a Lewis acid in CH<sub>2</sub>Cl<sub>2</sub>. These carbonato-derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH<sub>2</sub>Cl<sub>2</sub>or phNO<sub>2</sub>. Cryoscopic measurements support tetranuclear structure for all of them. Electronic spectra in the near infrared with high molecular absorptivity may be explained for tetranuclear cuban structure to fulfil 3 halo-ligands for each copper centre in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>]. The EPR spectra for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] complexes are axial type of spectra (d<sub>x2-y2</sub> G.S) suggesting elongated tetragonal distortion for all of them. Cyclic voltammograms for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] are irreversible in character. These tetranuclear carbonato complexes show catalytical activity. They initiate the oxidation of 2,6-dimethylphenol (DMP) to 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ).展开更多
A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in...A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.展开更多
The reaction of 5-(2-furanimino)-8-hydroxylquinoline(HL)and RE(dbm)_(3)·2H_(2)O(Hdbm=1,3-diphenyl-1,3-propanedione)afforded[RE_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)](RE=Y(1),Dy(2)),while under the same reaction cond...The reaction of 5-(2-furanimino)-8-hydroxylquinoline(HL)and RE(dbm)_(3)·2H_(2)O(Hdbm=1,3-diphenyl-1,3-propanedione)afforded[RE_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)](RE=Y(1),Dy(2)),while under the same reaction conditions,but with the replacement of the co-ligand,another series of tetranuclear complexes,[RE_(4)(acac)_(4)(L)_(6)(μ_(3)-OH)_(2)]·(CH_(3)CN)_(n)(n=2 for RE=Y(3),Dy(4),Ho(5);n=0 for RE=Tb(6);Hacac=acetylacetone),were obtained.Alternating current susceptibility measurements reveal that 2 displays single-molecule-magnet behavior with an effective energy barrier of U_(eff)=117.4 K(τ_(0)=1.79×10^(-8)s)under a zero direct-current field,while 4 presents two distinct slow magnetic relaxation processes with effective energy barriers of U_(eff)=162.1 K for the fast relaxation(FR)process(τ_(0)=8.53×10^(-11)s)and U_(eff)=165.3 K for the slow relaxation(SR)process(τ_(0)=1.14×10^(-9)s),which demonstrates that subtle changes of the coordination environment can drastically influence the overall magnetic properties.展开更多
One novel Co（II） coordination polymer, namely [Co4（L）6（NO3）2] （1） was prepared by solvothermal reactions of Co（NO3）2 with a （E）-2-[2-（3-thienyl）ethenyl]-8-quinolinol ligand （HL）, which has been determi...One novel Co（II） coordination polymer, namely [Co4（L）6（NO3）2] （1） was prepared by solvothermal reactions of Co（NO3）2 with a （E）-2-[2-（3-thienyl）ethenyl]-8-quinolinol ligand （HL）, which has been determined by single-crystal X-ray diffraction analyses and further characterized by means of elemental analyses, IR spectra, PXRD and thermogravimetric analyses （TGA）. The core structure of complex 1 is an incomplete dicubane-like tetranuclear Co（II） cluster, which is surrounded by six 8-hydroxy-quinolinate-based ligands and two nitrate ligands. Weak S-O interactions between the thienyl groups and nitrate ligands extend the adjacent tetranuclear CoOI） clusters into a supramolecular （4, 4） net structure. Magnetic measurement indicates that the coupling within both molecules is overall antiferromagnetic.展开更多
Two tetranuclear lanthanide complexes with the formulas[Dy_(4)(HL)_(4)(OAc)_(2)(H_(2)O)_(2)]·2Et_(3)NH·2CH_(3)CN(1)and[Gd_(4)(HL)_(4)(OAc)_(2)(H_(2)O)_(2)]·2Et_(3)NH·2CH_(3)OH·4CH_(3)CN(2)(H_(...Two tetranuclear lanthanide complexes with the formulas[Dy_(4)(HL)_(4)(OAc)_(2)(H_(2)O)_(2)]·2Et_(3)NH·2CH_(3)CN(1)and[Gd_(4)(HL)_(4)(OAc)_(2)(H_(2)O)_(2)]·2Et_(3)NH·2CH_(3)OH·4CH_(3)CN(2)(H_(4)L=N,N’-bis(3-hydroxylsalicylidene)benzene-1,2-diamine)were structurally and magnetically characterized.Dynamic magnetic studies revealed that complex 1 exhibits two distinct slow magnetic relaxation processes under a zero direct current(dc)field and the extracted energy barriers(U_(eff))of the low-temperature and high-temperature relaxation processes reach 207(2)K and 353(3)K,respectively,which are among the highest U_(eff) values of reported tetranuclear dysprosium molecular nanomagnets.More strikingly,as for complex 1,the open hysteresis loop behavior is detected until 5 K(6.5 K for the diluted sample),and a coercive field of 453 Oe is observed at 1.8 K,which is unusually seen in tetranuclear lanthanide single-molecule magnets.Further magnetic studies of diluted samples combined with ab initio calculation indicate that the Dy^(Ⅲ)–Dy^(Ⅲ) interactions play a crucial role in suppressing quantum tunneling of magnetization and consequently resulted in the bulk magnet-like hysteresis behavior.Additionally,the Gd-congener 2 displays the magnetocaloric effect(MCE)with a magnetic entropy change(−ΔS_(m))of 20.8 J kg^(-1) K^(−1) at 2 K for ΔH=7 T.展开更多
A metal-organic coordination polymer [ZnE.s（phen）（BDC）2（OH）]2 （phen = 1,10- phenanthroline, BDC = benzene-1,4-dicarboxylic acid） 1 has been hydrothermally synthesized and structurally characterized by single-c...A metal-organic coordination polymer [ZnE.s（phen）（BDC）2（OH）]2 （phen = 1,10- phenanthroline, BDC = benzene-1,4-dicarboxylic acid） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The complex crystallizes in the triclinic system, space group PI with a = 11.199（2）, b = 11.593（2）, c = 11.865（3）/A, α= 99.330（1）, β = 111.506（1）, γ = 104.804（1）^o, V= 1328.4（5）A^3, Dc= 1.722 g/cm^3, Z = 1, Mr = 1377.82, F（000） = 692,μ（MoKa） = 2.306 mm^-1, S = 1.093, R= 0.0281 and wR = 0.0756 for 4179 observed reflections （I 〉 2σ（/））. The coordination polyhedron around Zn（II） can be described as a tetrahedron, trigonal bipyramid and octahedron. It is worth noting that the crystal structure of 1 is composed of tetranuclear zinc clusters linked by {ZnO6} units.展开更多
A family of fourteen tetranuclear,3d-4f heterometallic nickel(Ⅱ)-lanthanide(Ⅲ)complexes of the hexaimine macrocycle(L^(Pr))^(6−),with general formula Ni_(3)^(Ⅱ)Ln^(Ⅲ)(L^(Pr))(NO_(3))_(3)·xsolvents(Ln^(Ⅲ)=La^...A family of fourteen tetranuclear,3d-4f heterometallic nickel(Ⅱ)-lanthanide(Ⅲ)complexes of the hexaimine macrocycle(L^(Pr))^(6−),with general formula Ni_(3)^(Ⅱ)Ln^(Ⅲ)(L^(Pr))(NO_(3))_(3)·xsolvents(Ln^(Ⅲ)=La^(Ⅲ),Ce^(Ⅲ),Pr^(Ⅲ),Nd^(Ⅲ),Sm^(Ⅲ),Eu^(Ⅲ),Gd^(Ⅲ),Tb^(Ⅲ),Dy^(Ⅲ),Ho^(Ⅲ),Er^(Ⅲ),Tm^(Ⅲ),Yb^(Ⅲ)or Lu^(Ⅲ)),were prepared in a one-pot synthesis using a 3:1:3:3 reaction of nickel(Ⅱ)acetate,the appropriate lanthanide(Ⅲ)nitrate,the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene(H_(2)L^(Ald))and 1,3-diaminopropane.In addition,three tetranuclear heterometallic nickel(Ⅱ)-lanthanide(Ⅲ)complexes of H_(2)L^(Ald),with general formula Ni_(3)^(Ⅱ)Ln^(Ⅲ)(L^(Ald))_(3)(NO_(3))_(3)·xsolvents,were deliberately prepared(Ln^(Ⅲ)=La^(Ⅲ),Dy^(Ⅲ)or Yb^(Ⅲ))as in effect they represent intermediates en route to the above macrocyclic complexes.Whilst single crystals of the macrocyclic complexes were not forthcoming,X-ray crystal structure determinations on Ni_(3)^(Ⅱ)Ln^(Ⅲ)(L^(Ald))_(3)(NO_(3))_(3)·xsolvents(Ln^(Ⅲ)=Dy^(Ⅲ)or Yb^(Ⅲ))confirmed that the large ten-coordinate lanthanide(Ⅲ)ion is bound in the central O_(6)pocket while the smaller six-coordinate nickel(Ⅱ)ions are bound in the outer O_(4)pockets.In all fourteen cases,addition of the diamine to this intermediate(all in one pot)gives the tetrametallic[3+3]macrocyclic product.The magnetic properties of all fourteen macrocyclic complexes were measured down to 1.8 K to check for Single-Molecule Magnet behaviour,but no slow dynamics of magnetisation was observed.展开更多
A novel tetranuclear complex[Pb_(4)L_(4)(CO_(3))_(2)]·4H_(2)O(1·4H_(2)O)is reported,which was obtained through the electrochemical oxidation of a lead anode under an ambient atmosphere in a CH_(3)CN:MeOH sol...A novel tetranuclear complex[Pb_(4)L_(4)(CO_(3))_(2)]·4H_(2)O(1·4H_(2)O)is reported,which was obtained through the electrochemical oxidation of a lead anode under an ambient atmosphere in a CH_(3)CN:MeOH solution of N’-isonicotinoylpicolinohydrazonamide(HL).CO_(3)^(2−) anions were formed through the conversion of aerial CO_(2) via the Pb^(2+)–L complex system under electrochemical conditions.The ligand L links two Pb^(2+) cations through the carbonyl oxygen atom,while the CO_(3)^(2−) anion links two Pb^(2+) cations through two monodentate and one bidentate oxygen atoms.The molecular structure of 1 is stabilized by a pair of Pb⋯O tetrel bonds formed with the bidentate oxygen atom of the CO_(3)^(2−) anion,while molecules of 1 are interlinked through reciprocalπ(chelate ring)⋯π(chelate ring),π(chelate ring)⋯π(noncovalent ring)and Pb⋯π(noncovalent ring)interactions,yielding a 1D supramolecular chain.The same reaction but under a nitrogen atmosphere yielded a novel mononuclear complex[PbL2]·MeOH·2H_(2)O(2·MeOH·2H_(2)O).In the structure of 2,each ligand L exhibits a tridentate coordination mode.Molecules of 2 are also interlinked through reciprocalπ(chelate ring)⋯π(chelate ring),π(chelate ring)⋯π(noncovalent ring)and Pb⋯π(noncovalent ring)interactions,similar to 1,yielding a 1D supramolecular chain.The energetic features of these assemblies were studied using DFT calculations.Additionally,QTAIM analysis was employed to characterize noncovalent contacts,including intermolecular Pb⋯N tetrel bonds.These tetrel bonds were further analyzed using the ELF and Laplacian of electron density 2D maps,which confirmed their noncovalent nature.The optical properties of the complexes were revealed using UV–vis and diffuse reflectance spectroscopy and spectrofluorometry.Both complexes were found to be emissive in a solution of MeOH.CIE-1931 chromaticity coordinates of(0.38,0.37)and(0.31,0.32)for 1·4H_(2)O and 2·MeOH·2H_(2)O,respectively,fall within the white gamut of the chromaticity diagram.展开更多
The synthesis,structure and magnetism of tetranuclear complexes,[Ln_(4)(LH_(2))_(2)(η^(1)-Piv)_(2)(η^(2)-Piv)_(2)(μ_(3)-O_(2))_(2)(H_(2)O)_(2)]·2MeOH(1,Ln=Gd^(Ⅲ);2,Ln=Tb^(Ⅲ);3,Ln=Dy^(Ⅲ);and 4,Ln=Er^(Ⅲ))(LH...The synthesis,structure and magnetism of tetranuclear complexes,[Ln_(4)(LH_(2))_(2)(η^(1)-Piv)_(2)(η^(2)-Piv)_(2)(μ_(3)-O_(2))_(2)(H_(2)O)_(2)]·2MeOH(1,Ln=Gd^(Ⅲ);2,Ln=Tb^(Ⅲ);3,Ln=Dy^(Ⅲ);and 4,Ln=Er^(Ⅲ))(LH_(4)=6-((bis(2-hydroxyethyl)amino)-N’-(2-hydroxybenzylidene)picolinohydrazide)(piv=pivalate ion)are reported.Interestingly,the formation of these tetranuclear assemblies is assisted by two side-on coordinating peroxide ligands which bind in aμ^(3)-η^(2):η^(2):η^(2) fashion.展开更多
基金Supported by the key Foundation of the Education Department of Hubei Province (No. D20081503)the foundation of the innovative group of the Education Department of Hubei Province (T200802)
文摘The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu（Ⅱ） in the proportion of 3：2：2 yields a new tetranuclear copper（Ⅱ） complex, [Cu2L]2（ClO4）2.2H2O（H3L= N,N＇-bis（4-（3＇-formyl-5＇-methylsalicyclidene）iminoethyl）-4-methyl-2,6-bimethyliminophenol）. The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673（11）, b = 12.0829（12）, c = 14.4834（15） А, α= 111.946（2）, β= 105.828（2）, γ = 99.583（2）°,V= 1618.5（3） А^3, Dc = 1.605 g/cm^3, Z = 2, Mr = 1564.26, F（000） = 800.0,μ（MoKa） = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections （I 〉 2σ（I））. The complex is a dimer of dinuclear copper（Ⅱ） acylic enantiomorph subunit [Cu2L]ClO4.H_2O, held together by π…π weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.
基金Supported by the National Key Project of Fundamental Research and the National Natural Science Foundation ofChina(No.29771001,
文摘The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.
基金Supported by the National Key Project of Fundamental Research and the National Natural Science Foundation ofChina(No.29771001,
文摘The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.
基金supported by the Scientific Research Common Program of Beijing Municipal Commission of Education (No. KM201010028008)
文摘The title tetranuclear complex,（μ4-oxo）-hexakis（μ2-chloro）-tetrakis（2-amino-1,3-thiazole-N）-tetra-copper（ii） [Cu4（μ4-O）（μ-Cl）6L4]（1,L=2-amino-1,3-thiazole） was synthesized by the reaction of CuCl2·2H2O with 2-amino-1,3-thiazole in methanol and characterized by IR spectra and X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=9.7137（2）,b=10.7005（2）,c=14.6505（2）,α=83.9550（10）,β=82.0930（10）,γ=67.1640（10）°,V=1387.84（4）3,Mr=883.43,Z=2,μ=3.927 mm-1,Dc=2.1144 g/cm3,F（000）=868,R=0.0332 and wR=0.0814.The complex contains a tetrahedron of four CuII atoms coordinating to a central μ4-O atom,with the six edges of the tetrahedron bridged by six Cl atoms.The Cu-O bond distances range from 1.910（2） to 1.918（2）,Cu-Cl from 2.3501（11） to 2.5924（10）,and Cu-Cu from 3.1003（6） to 3.1663（6）.The coordination geometries of the four coppers distort from trigonal bipramid to tetragonal pyramid with different distortion factors.The free animo groups of the ligands result in a lot of N-H···Cl and N-H···N intra-and intermolecular hydrogen bonds.
基金Supported by the National Natural Science Foundation of China(Nos. 20476011 and 20371007).
文摘The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.
基金Supported by the Natural Science Foundation of Jilin Province (No. 20060516)the Doctoral Foundation of Jilin Normal University (No. 2006006 and No. 2007009)+1 种基金the Science and Technology Institute Foundation of Siping City (No. 2005016)the Subject and Base Construction Foundation of Jilin Normal University (No. 2006041)
文摘A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal gravimetry （TG）, fluorescent emission and single-crystal X-ray diffraction. Its crystal structure is of monoclinic, space group P2 1/c with a = 9.8897（8）, b = 14.2506（12）, c = 26.384（2） ,A, β = 94.8940（10）°, V = 3704.8（5） A3 Z = 2, C86H52N16O16S2Zn4, Mr = 1891.04, Dc = 1.695 g/cm^3, μ= 1.423 mm^-1, F（000） = 1920, GOOF = 1.039, the final R = 0.0358 and wR = 0.0872 for 6038 observed reflections with I 〉 2σ（I）. In 1, ＂cage-like＂ tetranuclear clusters of [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] are further stacked through π-π interactions to generate a 3D supramolecular network.
基金The project supported by the National Natural Science Foundation of China
文摘The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central μ_4-O atom and the four Nd atoms.The results of calculation show that the μ_4-O atom uses its sp^3 valence orbitals to contribute four O-Nd bonding MOs with character of multicenter bond apparent- ly.The Mulliken population analysis shows that the overlap population between Nd atoms is almost equal to zero,therefore there is no direct metal-metal bond between Nd atoms.The coordination number of Nd in the complex is discussed briefly.
文摘The preparation and characterization of [CrnFe4-nO2(O2CMe)7(bipy)2]Cl (1, n=0; 2, n=2; 3, n=4, bipy=2,2'-bipyridine) are described. The three complexes (1, 2 and 3) are obtained by tipyridine-mediated conversion of trinuclear [CrnFe3-nO(O2CMe)6(H2O)3]+(1, n=0; 2, n=1;3, n=3), and crystallized as three of approximate isomorphs. Crystal 2 is monoclinic with space group C2/c, a=27.454(5)A, b=11.789(1)A, c=16.570(3)A, B=118.78(1), V=4700.8A, z=4, u(MoKa)=11.64cm-1, F(000)=2056, final R=0.058 and Rw=0.066 for 3479 reflections with I > 3o(I). The Fe and Cr atoms in the cation are all +3 oxide state and disordered in the lattice, which is also supported by its Mossbauer studies. The [Cr2Fe2O2]8+ core can be thought of as being derived from two edge-sharing M3O units (M=Fe or Cr), and as a butterfly-like structure. The cations' structure of all three crystals are similar to each other and have C2 symmetry. The species are characterized by IR spectra and magnetic techniques, with particular emphasis on differentiation of coordination bond strengths and electronic environment of metal atoms in these complexes.
文摘A new tetranuclear silver（I） complex with the formula of [Ag4（MMPzA）2（dmPz）4（H2DPC）2]（H2O）4（1, MMPz A = mono（3,5-bimethyl-pyrazolmethyl）amine）, dm Pz = 3,5-dimethylpyrazole, H2DPC = pyridine-3,4-dicarboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction method. The title complex crystallizes in the triclinic system, space group P1 with a = 10.5532（13）, b = 11.5071（18）, c = 13.3951（17） A, α = 97.3190（10）, β = 106.7360（10）, γ = 108.0770（10）o, V = 1438.3（3） A3, Z = 1, Dc = 1.691 g/cm3, F（000） = 736, μ = 1.421 mm-1, the final R = 0.0400 and w R = 0.0942 for 5097 observed reflections（I 〉 2σ（I））. The intermolecular hydrogen bonding interaction extends the complex into a 1D chain structure. In addition, the complex was tested in vitro for its antibacterial activity and it exhibited significant activity, especially against penicillium.
文摘In this work, novel oxidative coupling complexes, [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] (n = 1 or 2, X = Cl or Br, Pip = piperidine), are synthesized from the reaction of well characterized Lewis base [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>O<sub>2</sub>] with carbon dioxide as a Lewis acid in CH<sub>2</sub>Cl<sub>2</sub>. These carbonato-derivatives are isolated as stable solids. They are easily soluble in aprotic solvents as CH<sub>2</sub>Cl<sub>2</sub>or phNO<sub>2</sub>. Cryoscopic measurements support tetranuclear structure for all of them. Electronic spectra in the near infrared with high molecular absorptivity may be explained for tetranuclear cuban structure to fulfil 3 halo-ligands for each copper centre in [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>]. The EPR spectra for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] complexes are axial type of spectra (d<sub>x2-y2</sub> G.S) suggesting elongated tetragonal distortion for all of them. Cyclic voltammograms for [(Pip)<sub>4n</sub>Cu<sub>4</sub>X<sub>4</sub>(CO<sub>3</sub>)<sub>2</sub>] are irreversible in character. These tetranuclear carbonato complexes show catalytical activity. They initiate the oxidation of 2,6-dimethylphenol (DMP) to 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ).
文摘A tetranuclear Ln(Ⅲ)-based complex:[Dy_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)]·CH_(3)CN(1)(HL=5-[(4-methylbenzylidene)amino]quinolin-8-ol,Hdbm=dibenzoylmethane)was manufactured and its structure was characterized in detail.Xray diffraction analysis shows that complex 1 belongs to the monoclinic crystal system and its space group is P2_1/n,which contains a rhombic Dy_(4)core.Magnetic measurements of 1 suggest it possesses extraordinary single-molecule magnet(SMM)behavior.Its energy barrier U_(eff)/k_(B)was 116.7 K,and the pre-exponential coefficient τ_(0)=1.05×10~(-8)s.CCDC:2359322.
基金National Natural Science Foundation of China(No.21571138,21473121)Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education,Nankai University,Opening Foundation)111 Plan project(B12015)。
文摘The reaction of 5-(2-furanimino)-8-hydroxylquinoline(HL)and RE(dbm)_(3)·2H_(2)O(Hdbm=1,3-diphenyl-1,3-propanedione)afforded[RE_(4)(dbm)_(4)(L)_(6)(μ_(3)-OH)_(2)](RE=Y(1),Dy(2)),while under the same reaction conditions,but with the replacement of the co-ligand,another series of tetranuclear complexes,[RE_(4)(acac)_(4)(L)_(6)(μ_(3)-OH)_(2)]·(CH_(3)CN)_(n)(n=2 for RE=Y(3),Dy(4),Ho(5);n=0 for RE=Tb(6);Hacac=acetylacetone),were obtained.Alternating current susceptibility measurements reveal that 2 displays single-molecule-magnet behavior with an effective energy barrier of U_(eff)=117.4 K(τ_(0)=1.79×10^(-8)s)under a zero direct-current field,while 4 presents two distinct slow magnetic relaxation processes with effective energy barriers of U_(eff)=162.1 K for the fast relaxation(FR)process(τ_(0)=8.53×10^(-11)s)and U_(eff)=165.3 K for the slow relaxation(SR)process(τ_(0)=1.14×10^(-9)s),which demonstrates that subtle changes of the coordination environment can drastically influence the overall magnetic properties.
基金Supported by the National Natural Science Foundation of China(No.21372051,61671162)the Science and Technology Planning Project of Guangdong Province(No.2013B021700001,2016A010103031)+1 种基金the Excellent Young Teacher Development Project of Universities in Guangdong Province(No.261532106)the Guangzhou Science and Technology Program(No.502150105)
文摘One novel Co（II） coordination polymer, namely [Co4（L）6（NO3）2] （1） was prepared by solvothermal reactions of Co（NO3）2 with a （E）-2-[2-（3-thienyl）ethenyl]-8-quinolinol ligand （HL）, which has been determined by single-crystal X-ray diffraction analyses and further characterized by means of elemental analyses, IR spectra, PXRD and thermogravimetric analyses （TGA）. The core structure of complex 1 is an incomplete dicubane-like tetranuclear Co（II） cluster, which is surrounded by six 8-hydroxy-quinolinate-based ligands and two nitrate ligands. Weak S-O interactions between the thienyl groups and nitrate ligands extend the adjacent tetranuclear CoOI） clusters into a supramolecular （4, 4） net structure. Magnetic measurement indicates that the coupling within both molecules is overall antiferromagnetic.
基金supported by the NSFC(no.22071047)the Heilongjiang Provincial Natural Science Foundation of China(LH2019B016).
文摘Two tetranuclear lanthanide complexes with the formulas[Dy_(4)(HL)_(4)(OAc)_(2)(H_(2)O)_(2)]·2Et_(3)NH·2CH_(3)CN(1)and[Gd_(4)(HL)_(4)(OAc)_(2)(H_(2)O)_(2)]·2Et_(3)NH·2CH_(3)OH·4CH_(3)CN(2)(H_(4)L=N,N’-bis(3-hydroxylsalicylidene)benzene-1,2-diamine)were structurally and magnetically characterized.Dynamic magnetic studies revealed that complex 1 exhibits two distinct slow magnetic relaxation processes under a zero direct current(dc)field and the extracted energy barriers(U_(eff))of the low-temperature and high-temperature relaxation processes reach 207(2)K and 353(3)K,respectively,which are among the highest U_(eff) values of reported tetranuclear dysprosium molecular nanomagnets.More strikingly,as for complex 1,the open hysteresis loop behavior is detected until 5 K(6.5 K for the diluted sample),and a coercive field of 453 Oe is observed at 1.8 K,which is unusually seen in tetranuclear lanthanide single-molecule magnets.Further magnetic studies of diluted samples combined with ab initio calculation indicate that the Dy^(Ⅲ)–Dy^(Ⅲ) interactions play a crucial role in suppressing quantum tunneling of magnetization and consequently resulted in the bulk magnet-like hysteresis behavior.Additionally,the Gd-congener 2 displays the magnetocaloric effect(MCE)with a magnetic entropy change(−ΔS_(m))of 20.8 J kg^(-1) K^(−1) at 2 K for ΔH=7 T.
基金The project was supported by the Education Office of Jilin Province (No. 0047)
文摘A metal-organic coordination polymer [ZnE.s（phen）（BDC）2（OH）]2 （phen = 1,10- phenanthroline, BDC = benzene-1,4-dicarboxylic acid） 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The complex crystallizes in the triclinic system, space group PI with a = 11.199（2）, b = 11.593（2）, c = 11.865（3）/A, α= 99.330（1）, β = 111.506（1）, γ = 104.804（1）^o, V= 1328.4（5）A^3, Dc= 1.722 g/cm^3, Z = 1, Mr = 1377.82, F（000） = 692,μ（MoKa） = 2.306 mm^-1, S = 1.093, R= 0.0281 and wR = 0.0756 for 4179 observed reflections （I 〉 2σ（/））. The coordination polyhedron around Zn（II） can be described as a tetrahedron, trigonal bipyramid and octahedron. It is worth noting that the crystal structure of 1 is composed of tetranuclear zinc clusters linked by {ZnO6} units.
基金supported by grants from the MacDiarmid Institute for Advanced Materials and Nanotechnology(including a PhD scholarship to SD)the University of Otago(including a PhD scholarship to HLCF)the award of a Julius von Haast Fellowship(RSNZ)to AKP,hosted by SB.
文摘A family of fourteen tetranuclear,3d-4f heterometallic nickel(Ⅱ)-lanthanide(Ⅲ)complexes of the hexaimine macrocycle(L^(Pr))^(6−),with general formula Ni_(3)^(Ⅱ)Ln^(Ⅲ)(L^(Pr))(NO_(3))_(3)·xsolvents(Ln^(Ⅲ)=La^(Ⅲ),Ce^(Ⅲ),Pr^(Ⅲ),Nd^(Ⅲ),Sm^(Ⅲ),Eu^(Ⅲ),Gd^(Ⅲ),Tb^(Ⅲ),Dy^(Ⅲ),Ho^(Ⅲ),Er^(Ⅲ),Tm^(Ⅲ),Yb^(Ⅲ)or Lu^(Ⅲ)),were prepared in a one-pot synthesis using a 3:1:3:3 reaction of nickel(Ⅱ)acetate,the appropriate lanthanide(Ⅲ)nitrate,the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene(H_(2)L^(Ald))and 1,3-diaminopropane.In addition,three tetranuclear heterometallic nickel(Ⅱ)-lanthanide(Ⅲ)complexes of H_(2)L^(Ald),with general formula Ni_(3)^(Ⅱ)Ln^(Ⅲ)(L^(Ald))_(3)(NO_(3))_(3)·xsolvents,were deliberately prepared(Ln^(Ⅲ)=La^(Ⅲ),Dy^(Ⅲ)or Yb^(Ⅲ))as in effect they represent intermediates en route to the above macrocyclic complexes.Whilst single crystals of the macrocyclic complexes were not forthcoming,X-ray crystal structure determinations on Ni_(3)^(Ⅱ)Ln^(Ⅲ)(L^(Ald))_(3)(NO_(3))_(3)·xsolvents(Ln^(Ⅲ)=Dy^(Ⅲ)or Yb^(Ⅲ))confirmed that the large ten-coordinate lanthanide(Ⅲ)ion is bound in the central O_(6)pocket while the smaller six-coordinate nickel(Ⅱ)ions are bound in the outer O_(4)pockets.In all fourteen cases,addition of the diamine to this intermediate(all in one pot)gives the tetrametallic[3+3]macrocyclic product.The magnetic properties of all fourteen macrocyclic complexes were measured down to 1.8 K to check for Single-Molecule Magnet behaviour,but no slow dynamics of magnetisation was observed.
基金supported by the grant from the Russian Science Foundation(No.24-23-00118)MICIU/AEI of Spain(PID2020-115637GB-I00,FEDER funds)for financial supportthe CTI(UIB)for computational facilities.
文摘A novel tetranuclear complex[Pb_(4)L_(4)(CO_(3))_(2)]·4H_(2)O(1·4H_(2)O)is reported,which was obtained through the electrochemical oxidation of a lead anode under an ambient atmosphere in a CH_(3)CN:MeOH solution of N’-isonicotinoylpicolinohydrazonamide(HL).CO_(3)^(2−) anions were formed through the conversion of aerial CO_(2) via the Pb^(2+)–L complex system under electrochemical conditions.The ligand L links two Pb^(2+) cations through the carbonyl oxygen atom,while the CO_(3)^(2−) anion links two Pb^(2+) cations through two monodentate and one bidentate oxygen atoms.The molecular structure of 1 is stabilized by a pair of Pb⋯O tetrel bonds formed with the bidentate oxygen atom of the CO_(3)^(2−) anion,while molecules of 1 are interlinked through reciprocalπ(chelate ring)⋯π(chelate ring),π(chelate ring)⋯π(noncovalent ring)and Pb⋯π(noncovalent ring)interactions,yielding a 1D supramolecular chain.The same reaction but under a nitrogen atmosphere yielded a novel mononuclear complex[PbL2]·MeOH·2H_(2)O(2·MeOH·2H_(2)O).In the structure of 2,each ligand L exhibits a tridentate coordination mode.Molecules of 2 are also interlinked through reciprocalπ(chelate ring)⋯π(chelate ring),π(chelate ring)⋯π(noncovalent ring)and Pb⋯π(noncovalent ring)interactions,similar to 1,yielding a 1D supramolecular chain.The energetic features of these assemblies were studied using DFT calculations.Additionally,QTAIM analysis was employed to characterize noncovalent contacts,including intermolecular Pb⋯N tetrel bonds.These tetrel bonds were further analyzed using the ELF and Laplacian of electron density 2D maps,which confirmed their noncovalent nature.The optical properties of the complexes were revealed using UV–vis and diffuse reflectance spectroscopy and spectrofluorometry.Both complexes were found to be emissive in a solution of MeOH.CIE-1931 chromaticity coordinates of(0.38,0.37)and(0.31,0.32)for 1·4H_(2)O and 2·MeOH·2H_(2)O,respectively,fall within the white gamut of the chromaticity diagram.
基金University Grants Commission(UGC),India,for the Senior Research Fellowship.S.K.S.and P.P.S.acknowledge the Department of Science and Technology for the Start-up Research Grant(SRG/2020/001323).S.K.S.thanks IIT Hyderabad for generous seed grant fundingThe support and resources provided by the PARAM Shivay Facility under the National Supercomputing Mission,Government of India at the Indian Institute of Technology,Varanasi,are gratefully acknowledged.F.P.,J.F.G.,and O.C.thank the European Research Council through the ERCCoG 725184 MULTIPROSMM(project no.725184)。
文摘The synthesis,structure and magnetism of tetranuclear complexes,[Ln_(4)(LH_(2))_(2)(η^(1)-Piv)_(2)(η^(2)-Piv)_(2)(μ_(3)-O_(2))_(2)(H_(2)O)_(2)]·2MeOH(1,Ln=Gd^(Ⅲ);2,Ln=Tb^(Ⅲ);3,Ln=Dy^(Ⅲ);and 4,Ln=Er^(Ⅲ))(LH_(4)=6-((bis(2-hydroxyethyl)amino)-N’-(2-hydroxybenzylidene)picolinohydrazide)(piv=pivalate ion)are reported.Interestingly,the formation of these tetranuclear assemblies is assisted by two side-on coordinating peroxide ligands which bind in aμ^(3)-η^(2):η^(2):η^(2) fashion.
