Two novel high valent complexes [M2(III, III)L(μ-OAc)2]·PF6 (M=Mn, Fe; 9) were prepared, where L was the tri-anion of 2,6-bis{[(2-hydroxy-3-(morpholin-4-yl methyl)-5-tert- butyl benzyl)(pyridyl-2-methyl)amino]...Two novel high valent complexes [M2(III, III)L(μ-OAc)2]·PF6 (M=Mn, Fe; 9) were prepared, where L was the tri-anion of 2,6-bis{[(2-hydroxy-3-(morpholin-4-yl methyl)-5-tert- butyl benzyl)(pyridyl-2-methyl)amino]methyl}-4-methyl phenol which contained additional phenolic, tert-butyl and morpholin-4-yl methyl groups compared to its parent [Mn2(II, II)(bpmp) (μ-OAc)2]·ClO4 (10). These improvements decreased the difference between the new model and (Mn)4 cluster (OEC in nature).展开更多
Three dinuclear Dy(Ⅲ)complexes,[Dy_(2)(tfa)_(4)L_(2)](1),[Dy_(2)(TTA)_(4)L_(2)](2)and[Dy_(2)(dbm)_(4)L_(2)·2CH_(3)CN·0.5H_(2)O](3)(tfa=trifluoroacetylacetonate,TTA=2-thenoyltrifluoroacetone,dbm=dibenzoylmet...Three dinuclear Dy(Ⅲ)complexes,[Dy_(2)(tfa)_(4)L_(2)](1),[Dy_(2)(TTA)_(4)L_(2)](2)and[Dy_(2)(dbm)_(4)L_(2)·2CH_(3)CN·0.5H_(2)O](3)(tfa=trifluoroacetylacetonate,TTA=2-thenoyltrifluoroacetone,dbm=dibenzoylmethane and HL=2-[((4-bromophenyl)-imino)methyl]-8-hydroxyquinoline,have been synthesized,and structurally and magnetically characterized.The Dy(Ⅲ)ions are eight-coordinated with two bidentate β-diketonate and two μ_(2)-O bridging 8-hydroxyquinoline Schiff base ligands.Magnetic studies reveal that 1-3 exhibit different magnetic relaxation behaviors with the anisotropic barriers of 9.61 K(1),54.81 K(2)and 30.98 K(3),respectively.The different magnetic relaxation behaviors of the three Dy_(2)complexes originate from the different chemical environments of the central Dy3+ions with different β-diketonate coligands.展开更多
A series of triiron clusters[Fe_(3)(CO)_(5)(κ^(2)-dppe)(μ-pdt^(R_(2)))(μ-pdt)]featuring different combinations of dithiolate bridges have been prepared by using dinuclear and mononuclear precursors,[Fe_(2)(CO)_(6)(...A series of triiron clusters[Fe_(3)(CO)_(5)(κ^(2)-dppe)(μ-pdt^(R_(2)))(μ-pdt)]featuring different combinations of dithiolate bridges have been prepared by using dinuclear and mononuclear precursors,[Fe_(2)(CO)_(6)(μ-xdt)](xdt=pdt,pdt^(Et_(2)),pdt^(Bn_(2)),adt^(Bn))and[Fe(CO)_(2)(κ^(2)-dppe)(κ^(2)-pdt)].Novel triiron compounds,featuring sterically crowded dithiolate bridges(pdt^(Et_(2)),pdt^(Bn_(2))),were spectroscopically and structurally characterized.Their protonation and redox behaviours are discussed.The effect of the dithiolate bridges on the electrochemical properties(oxidation and reduction)of the complexes[Fe_(3)(CO)_(5)(κ^(2)-dppe)(μ-xdt)(μ-pdt)]has been examined by cyclic voltammetry and rationalized by DFT calculations.Studies on the protonation of these species and their proton reduction behaviour were considered.展开更多
The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of...The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.展开更多
Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2’,3’-c:3’,2'-h:2'’,3’'-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3...Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2’,3’-c:3’,2'-h:2'’,3’'-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3-dione were synthesized and their photoluminescence properties were investigated. After ligand-mediated excitation, all the complexes showed the characteristic luminescence of the corresponding Ln(III) ions in the visible and NIR regions attributed to energy transfer from the ligands to the metal center. For Eu...展开更多
This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4...This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).展开更多
Four dinuclear amino acid cadmium(II)complexes[Cd2(tren)2(dl-alaninato)](ClO4)3·H2O(I),[Cd2(tren)2·(l-alaninato)](ClO4)3·H2O(II),[Cd2(tren)2(dl-phenylalaninato)](ClO4)3(III)and[Cd2(tren)2(l-phenylalanin...Four dinuclear amino acid cadmium(II)complexes[Cd2(tren)2(dl-alaninato)](ClO4)3·H2O(I),[Cd2(tren)2·(l-alaninato)](ClO4)3·H2O(II),[Cd2(tren)2(dl-phenylalaninato)](ClO4)3(III)and[Cd2(tren)2(l-phenylalaninato)]·(ClO4)3(IV),constructed from mixed ligands of tris(2-aminoethyl)amine(tren)and racemic or natural amino ac ids(amino acids=dl or l-alanine,and dl or l-phenylalanine),have been synthesized and characterized by X-ray crys tallography.The structural analysis of complexes I and III reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual(N,O,O′)-bridged mode,resulting in asymmetric chromo phores of CdN4O and CdN5O in complex I,CdN4O2 and CdN5O in complex III,respectively.The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined.The reaction proceeded smoothly to afford the correspondingβ-hydroxy ketones in up to 99%yield.Moreover,the dias tereoselectivity of the reaction favors the formation of the syn-isomers.展开更多
Dinuclear Cu(Ⅱ)complexes(Cu,LCl4).2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis.(Cu2I-Cl4).2H2O,C20 H40N6Cu2Cl4O2,Mr=665.54,monoclinic,6 for 188l observed reflections with I>3(I...Dinuclear Cu(Ⅱ)complexes(Cu,LCl4).2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis.(Cu2I-Cl4).2H2O,C20 H40N6Cu2Cl4O2,Mr=665.54,monoclinic,6 for 188l observed reflections with I>3(I).Cu2L'Cl4,C20H36N6Cu2Cl4,M.=629.41,monoclinic,for 1330 observed reflections with I>3(I).In both complexes the stereo-chemistry about Cu(Ⅱ)is 5-coordinated with two secondary amine N atoms and twoCl-occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom.The pair of Cl'attached to the two Cu(Ⅱ)are held in anti configuration.展开更多
Superior neutral or cationic dinuclear gold(Ⅰ)N-heterocyclic carbene(NHC)complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom.The novel cation...Superior neutral or cationic dinuclear gold(Ⅰ)N-heterocyclic carbene(NHC)complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom.The novel cationic dinuclear gold(Ⅰ)complex 4a(BF5-Au)with bis-NHC ligands exhibited potent anti-liver cancer capacity in vitro and in vivo.The Hyper7 sensor was first used to analyze the sites of reactive oxygen species(ROS)generation by BF5-Au,showing that ROS were preferably generated in mitochondria and endoplasmic reticulum.Mechanism studies showed that BF5-Au could induce immunogenic cell death(ICD)via ROS-driven endoplasmic reticulum stress(ERS).However,targeting a single type of immune cell seems insufficient to reverse the immunosuppressive circumstances.Further investigation indicated that BF5-Au could enhance antitumor immune responses by inducing ferroptosis and polarizing macrophages to M1-like types.Overall,BF5-Au could inhibit tumor growth and remodel the tumor microenvironment via ROS-driven ERS and ferroptosis,which is expected to be a promising chemoimmunotherapy for cancer treatment.展开更多
Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, ...Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P 1. The coordination geometry around Ln（Ⅲ） ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb（Ⅲ） in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.展开更多
Dinuclear[M(H_(3)L^(1,2,4))]_(2)(M=Dy,Dy_(2);M=Ho,Ho_(2))complexes were isolated from an heptadentate aminophenol ligand.The crystal structures of Dy_(2)·2THF,and the pyridine adducts Dy_(2)·2Py and Ho_(2)&#...Dinuclear[M(H_(3)L^(1,2,4))]_(2)(M=Dy,Dy_(2);M=Ho,Ho_(2))complexes were isolated from an heptadentate aminophenol ligand.The crystal structures of Dy_(2)·2THF,and the pyridine adducts Dy_(2)·2Py and Ho_(2)·2Py,show that the complexes are dinuclear,with unsupported double phenoxide bridges,and that the N_(4)O_(4) environment of the Ln^(Ⅲ) centres is distorted triangular dodecahedral.The magnetic analysis of Dy_(2) and Ho_(2) shows that Dy_(2) is a single molecular magnet(SMM),with a thermal-activated zero-field effective energy barrier(U_(eff))of 367.7 K,the largest barrier shown by double phenoxide-bridged dinuclear dysprosium complexes to date.Ho_(2) is one of the scarce dinuclear complexes showing frequency-dependence for the out-of-phase component of susceptibility,although it does not even show field-induced SMM behaviour above 2 K.Ab initio calculations were performed in order to shed light on the magnetic dynamics of the complexes,and these studies support the experimental magnetic results.展开更多
The electronic[Xe]4f^(13) configurations of Yb(Ⅲ)ions generate a variety of electronic energy levels,resulting in the fantastic optical and magnetic multifunctional properties of Yb(Ⅲ)complexes.Here,2-hydroxy-3-meth...The electronic[Xe]4f^(13) configurations of Yb(Ⅲ)ions generate a variety of electronic energy levels,resulting in the fantastic optical and magnetic multifunctional properties of Yb(Ⅲ)complexes.Here,2-hydroxy-3-methoxy benzoic acid(H_(2)MBA)was used to construct two dinuclear and one-dimensional Yb(Ⅲ)complexes namely[Yb_(2)(HMBA)_(2)(MBA)_(2)(DMF)_(2)(H_(2)O)_(2)]·6H_(2)O(1,DMF=N,N-dimethylformamide)and[NH_(4)][Yb(HMBA)_(4)](2).Fluorescence measurements reveal that H_(2)MBA can sensitize the characteristic near-infrared luminescence of Yb(Ⅲ).Magnetic susceptibility measurements show that the two Yb(Ⅲ)complexes are field-induced single-molecule magnets(SMMs)with anisotropy barriers of 18(1)cm^(-1) and 20(1)cm^(-1) for 1 and 2,respectively.The magnetism-luminescence-structure correlations as well as relaxation pathways are investigated by ab initio calculations and fluorescence spectrometry.展开更多
A dinuclear complex Cd2（dnba）4（pyridine）4 （dnba = 3,5-dinitrobenzoate） has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, D...A dinuclear complex Cd2（dnba）4（pyridine）4 （dnba = 3,5-dinitrobenzoate） has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, DSC and TG-DTG techniques. The complex with empirical formula C48H32Cd2NI2024 （Mr = 692.83） crystallizes in monoclinic, space group P21/n with a - 12.0344（14）, b = 10.5752（13）, c = 21.578（3） A, β = 104.150（2）°, V = 2662.8（6） A^3, Z = 2, D, = 1.728 g/cm^3,μ（MoKa） = 0.897 mm^-1, F（000） = 1384, S = 1.016 and （△/σ）max = 0.001. R = 0.0638 and wR = 0.0737 for all data; the final R = 0.0337 and wR = 0.0644. In this complex, four carboxylates are bidentate-or chelate-coordinated with the Cd（Ⅱ） centers to give the dinuclear structure. The other coordination positions of Cd（Ⅱ） are occupied by the lone pair electrons from N of four pyridines. Thermal analyses DSC and TG-DTG have been used to determine the thermal decomposition mechanism of the title complex.展开更多
5,6,7-Trihydroquinolin-8-one was condensed with the corresponding benzidine to give N,N′-bis（5,6,7-trihydroquinolin-8-ylidene）-[1,1′-biphenyl]-4,4′-diamine derivatives（L1–L3）. The ligands were reacted with two...5,6,7-Trihydroquinolin-8-one was condensed with the corresponding benzidine to give N,N′-bis（5,6,7-trihydroquinolin-8-ylidene）-[1,1′-biphenyl]-4,4′-diamine derivatives（L1–L3）. The ligands were reacted with two equivalents of Ni Cl2·6H2O in a mixture of Et OH and CH2Cl2 to afford the corresponding dinickel（II） chloride complexes（Ni1-Ni3）. The organic compounds were completely characterized, whilst the bi-metallic complexes were characterized by FTIR spectra and elemental analysis. These nickel complexes exhibited high activities towards ethylene polymerization in the presence of either MAO or Me2AlCl, maintaining a high activity over a prolonged period. The obtained polyethylenes were confirmed as having low molecular weights by GPC analysis.展开更多
The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs...The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.展开更多
A new dinuclear manganese complex [Mn2（L）2（2,2＇-bipy）2（H2O）512·3H2O has been synthesized with MnSO4·H2O, 2,2＇-bibenzoic acid （H2L） and 2,2＇-bipyridine（2,2＇-bipy） in the mixed solvent ethanol an...A new dinuclear manganese complex [Mn2（L）2（2,2＇-bipy）2（H2O）512·3H2O has been synthesized with MnSO4·H2O, 2,2＇-bibenzoic acid （H2L） and 2,2＇-bipyridine（2,2＇-bipy） in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group Pi with a = 9.9944（10）, b = 21.939（2）, c = 25.628（3） A, a = 108.429（3）, β = 100.613（4）, 7 = 102.821（3）°, V = 4997.9（9） A3, Dc= 1.355 g/cm^3, Z = 2, F（000） = 2108, GOOF = 1.074, the R= 0.0626 and wR= 0.1531. The structure of the complex contains two [Mn2（L）2（2,2＇-bipy）2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.展开更多
A new 4-chlorobenzoic acid bridge Co（Ⅱ ） complex [[Co2（2,2＇-bpy）2（μ-L）e（L）2（μ-H2O）] （HL = 4-chlorobenzoic acid） has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysi...A new 4-chlorobenzoic acid bridge Co（Ⅱ ） complex [[Co2（2,2＇-bpy）2（μ-L）e（L）2（μ-H2O）] （HL = 4-chlorobenzoic acid） has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537（5）, b = 16.212（3）, c = 15.306（3） A, β= 124.37（3）°, V= 4616.1（16）A3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, p = 1.012 mm-1, F（000） = 2176, the final R = 0.0338 and wR= 0.0810. The title complex is composed of dinuclear [Co2（2,2＇-bpy）2（μ-L）2（L）2（μ-HaO）] molecules. Each Co（Ⅱ ） atom is coordinated by two nitrogen atoms from one 2,2’-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co（Ⅱ） atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.展开更多
A new ligand 2-（4,5-dihydro-2-thiazolyl）-6-methoxyl benzothiazole and its new dinuclear Co（II） coordination complex [Co（C11H10N2OS2）Cl2]2·2CHCl3 （1） have been synthesized and characterized. Complex 1 was ...A new ligand 2-（4,5-dihydro-2-thiazolyl）-6-methoxyl benzothiazole and its new dinuclear Co（II） coordination complex [Co（C11H10N2OS2）Cl2]2·2CHCl3 （1） have been synthesized and characterized. Complex 1 was synthesized by the reaction of Co（II） salt with 2-（4,5-dihydro- 2-thiazolyl）-6-methoxyl benzothiazole under room-temperature evaporation condition and struc- turally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The supramolecular network of complex 1 is stabilized by the presence of intermolecular interaction, such as C-H···Cl hydrogen bonding and π-π stacking. The complex crystallizes in triclinic, space group P1 with a = 8.3288（12）, b = 10.5273（15）, c = 10.822（2）, α = 93.416（3）, β = 90.864（3）, γ = 94.890（3）o, V = 943.60（2）3, Z = 2, Dc = 1.758 g/cm3, F（000） = 498 and μ = 1.840 mm-1. The final complex [Co（C11H10N2OS2）Cl2]2·2CHCl3 is a diplex bridged dinuclear complex consisting of two Co（II） ions, two ligands, two bridging Cl- anions and two terminal Cl- anions.展开更多
Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we de...Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.展开更多
A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)...A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.展开更多
基金supported by"973 program"of the Ministry of Science and Technology of Chinathe National Natural Science Foundation of China(Project 20376010,20128005)B.A.and L.S.thank the Swedish Energy Agency and the Swedish Research Council for financial support.
文摘Two novel high valent complexes [M2(III, III)L(μ-OAc)2]·PF6 (M=Mn, Fe; 9) were prepared, where L was the tri-anion of 2,6-bis{[(2-hydroxy-3-(morpholin-4-yl methyl)-5-tert- butyl benzyl)(pyridyl-2-methyl)amino]methyl}-4-methyl phenol which contained additional phenolic, tert-butyl and morpholin-4-yl methyl groups compared to its parent [Mn2(II, II)(bpmp) (μ-OAc)2]·ClO4 (10). These improvements decreased the difference between the new model and (Mn)4 cluster (OEC in nature).
基金supported financially by the National Natural Science Foundation of China(no.21271137,21571138 and 21561014).
文摘Three dinuclear Dy(Ⅲ)complexes,[Dy_(2)(tfa)_(4)L_(2)](1),[Dy_(2)(TTA)_(4)L_(2)](2)and[Dy_(2)(dbm)_(4)L_(2)·2CH_(3)CN·0.5H_(2)O](3)(tfa=trifluoroacetylacetonate,TTA=2-thenoyltrifluoroacetone,dbm=dibenzoylmethane and HL=2-[((4-bromophenyl)-imino)methyl]-8-hydroxyquinoline,have been synthesized,and structurally and magnetically characterized.The Dy(Ⅲ)ions are eight-coordinated with two bidentate β-diketonate and two μ_(2)-O bridging 8-hydroxyquinoline Schiff base ligands.Magnetic studies reveal that 1-3 exhibit different magnetic relaxation behaviors with the anisotropic barriers of 9.61 K(1),54.81 K(2)and 30.98 K(3),respectively.The different magnetic relaxation behaviors of the three Dy_(2)complexes originate from the different chemical environments of the central Dy3+ions with different β-diketonate coligands.
基金CNRS(Centre National de la Recherche Scientifique),the University of Brest,and the University of Milano-Bicocca are acknowledged for financial support。
文摘A series of triiron clusters[Fe_(3)(CO)_(5)(κ^(2)-dppe)(μ-pdt^(R_(2)))(μ-pdt)]featuring different combinations of dithiolate bridges have been prepared by using dinuclear and mononuclear precursors,[Fe_(2)(CO)_(6)(μ-xdt)](xdt=pdt,pdt^(Et_(2)),pdt^(Bn_(2)),adt^(Bn))and[Fe(CO)_(2)(κ^(2)-dppe)(κ^(2)-pdt)].Novel triiron compounds,featuring sterically crowded dithiolate bridges(pdt^(Et_(2)),pdt^(Bn_(2))),were spectroscopically and structurally characterized.Their protonation and redox behaviours are discussed.The effect of the dithiolate bridges on the electrochemical properties(oxidation and reduction)of the complexes[Fe_(3)(CO)_(5)(κ^(2)-dppe)(μ-xdt)(μ-pdt)]has been examined by cyclic voltammetry and rationalized by DFT calculations.Studies on the protonation of these species and their proton reduction behaviour were considered.
基金Project supported by National Natural Science Foundation of China (21601143)Natural Science Foundation of Shaanxi Province (2021JM309)+2 种基金Open Funds of the State Key Laboratory of Rare Earth Resource of Changchun Institute of Applied Chemistry (RERU2021012)Science and Technology Innovation Team Program of Shaanxi Province (2022TD-32) and DST/SERB (CRG/2018/000430,DST/SJF/CSA03/2018-10SB/SJF/2019-20/12)。
文摘The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.
基金Project supported by the National Natural Science Foundation of China (20701019, 20971067, 20721002)the Natural Science Foundation of Ji-angsu Province (BK2008257)the Major State Basic Research Development Program (2006CB806104, 2007CB925103)
文摘Several dinuclear lanthanide complexes of Ln2(HTH)6TPPHZ (Ln=Eu, Sm, Er, Nd, Yb, Ho; TPPHZ=Tetrapyrido (3,2-a:2’,3’-c:3’,2'-h:2'’,3’'-j) phenazine; HTH=4,5,5,6,6,6-heptafluroro-1-(2-thienyl)hexane-1,3-dione were synthesized and their photoluminescence properties were investigated. After ligand-mediated excitation, all the complexes showed the characteristic luminescence of the corresponding Ln(III) ions in the visible and NIR regions attributed to energy transfer from the ligands to the metal center. For Eu...
文摘This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).
基金Supported by the National Natural Science Foundation of China(No.21001047)the Self-determined Research Funds of Central China Normal University from the Colleges’Basic Research and Operation of Ministry of Education,China(No.CCNU10A01010)
文摘Four dinuclear amino acid cadmium(II)complexes[Cd2(tren)2(dl-alaninato)](ClO4)3·H2O(I),[Cd2(tren)2·(l-alaninato)](ClO4)3·H2O(II),[Cd2(tren)2(dl-phenylalaninato)](ClO4)3(III)and[Cd2(tren)2(l-phenylalaninato)]·(ClO4)3(IV),constructed from mixed ligands of tris(2-aminoethyl)amine(tren)and racemic or natural amino ac ids(amino acids=dl or l-alanine,and dl or l-phenylalanine),have been synthesized and characterized by X-ray crys tallography.The structural analysis of complexes I and III reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual(N,O,O′)-bridged mode,resulting in asymmetric chromo phores of CdN4O and CdN5O in complex I,CdN4O2 and CdN5O in complex III,respectively.The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined.The reaction proceeded smoothly to afford the correspondingβ-hydroxy ketones in up to 99%yield.Moreover,the dias tereoselectivity of the reaction favors the formation of the syn-isomers.
基金supported by the NNSF of Chinathe Special Funds of State Education Committee for Doctorate Scientific Research.
文摘Dinuclear Cu(Ⅱ)complexes(Cu,LCl4).2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis.(Cu2I-Cl4).2H2O,C20 H40N6Cu2Cl4O2,Mr=665.54,monoclinic,6 for 188l observed reflections with I>3(I).Cu2L'Cl4,C20H36N6Cu2Cl4,M.=629.41,monoclinic,for 1330 observed reflections with I>3(I).In both complexes the stereo-chemistry about Cu(Ⅱ)is 5-coordinated with two secondary amine N atoms and twoCl-occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom.The pair of Cl'attached to the two Cu(Ⅱ)are held in anti configuration.
基金supported by the National Natural Science Foundation of China(No.82173684)the Priority Academic Program Development of Jiangsu Higher Education Institutions(Integration of Chinese and Western Medicine),High level key discipline construction project of the National Administration of Traditional Chinese Medicine-Resource Chemistry of Chinese Medicinal Materials(No.zyyzdxk-2023083)+1 种基金the Key R&D Program of Jiangsu Province(No.BE2023840)Yunnan Provincial Science and Technology Talent and Platform Program(No.202405AF140031)。
文摘Superior neutral or cationic dinuclear gold(Ⅰ)N-heterocyclic carbene(NHC)complexes with antitumor and tumor microenvironment regulation functions were developed by introducing an additional gold atom.The novel cationic dinuclear gold(Ⅰ)complex 4a(BF5-Au)with bis-NHC ligands exhibited potent anti-liver cancer capacity in vitro and in vivo.The Hyper7 sensor was first used to analyze the sites of reactive oxygen species(ROS)generation by BF5-Au,showing that ROS were preferably generated in mitochondria and endoplasmic reticulum.Mechanism studies showed that BF5-Au could induce immunogenic cell death(ICD)via ROS-driven endoplasmic reticulum stress(ERS).However,targeting a single type of immune cell seems insufficient to reverse the immunosuppressive circumstances.Further investigation indicated that BF5-Au could enhance antitumor immune responses by inducing ferroptosis and polarizing macrophages to M1-like types.Overall,BF5-Au could inhibit tumor growth and remodel the tumor microenvironment via ROS-driven ERS and ferroptosis,which is expected to be a promising chemoimmunotherapy for cancer treatment.
基金the National Natural Science Foundation of China (20772037)the Natural Science Foundation of Guangdong Province (06025033)
文摘Two dinuclear compounds [Ln2（acetate）6（H2O）4]-4H2O （Ln=Tb（1）, Sm（2）） were obtained by the hydrothermal reaction of Ln2O3 with malonic acid at 150 ℃. Both compounds were characterized by elemental analyses, infrared spectra, and single crystal X-ray diffraction. The results showed that complexes 1 and 2 were isomorphous and crystallize in triclinic space group P 1. The coordination geometry around Ln（Ⅲ） ions in the complexes 1 and 2 was a distorted tricapped trigonal prism with a nine coordination. In the crystal, the molecular organization was further stabilized by well-defined weak hydrogen bonding interactions between the neutral dinuclear molecular units that led to the formation of a three-dimensional network. The fluorescence properties of the two complexes 1 and 2 in organic solvents were also studied. The results show that the ligand acetate favored energy transfer to the emitting energy level of Tb（Ⅲ） in complex 1. Some factors that influence the fluorescent intensity were also discussed in the article.
基金the Spanish Ministerio de Innovación,Ciencia y Universidades(PGC2018-102052-B-C21,PGC2018-093863-B-C21 and MDM-2017-0767)for financial supportXunta de Galicia for his Ph.D.fellowship(ED481A-2018/136)+1 种基金the Junta de Andalucía(FQM-195 and the Project financed by FEDER funds A-FQM-172-UGR18)Generalitat de Catalunya for an ICREA Academia award and for the SGR2017-1289 grant,and S.G.C.for a Beatriu de Pinòs grant.
文摘Dinuclear[M(H_(3)L^(1,2,4))]_(2)(M=Dy,Dy_(2);M=Ho,Ho_(2))complexes were isolated from an heptadentate aminophenol ligand.The crystal structures of Dy_(2)·2THF,and the pyridine adducts Dy_(2)·2Py and Ho_(2)·2Py,show that the complexes are dinuclear,with unsupported double phenoxide bridges,and that the N_(4)O_(4) environment of the Ln^(Ⅲ) centres is distorted triangular dodecahedral.The magnetic analysis of Dy_(2) and Ho_(2) shows that Dy_(2) is a single molecular magnet(SMM),with a thermal-activated zero-field effective energy barrier(U_(eff))of 367.7 K,the largest barrier shown by double phenoxide-bridged dinuclear dysprosium complexes to date.Ho_(2) is one of the scarce dinuclear complexes showing frequency-dependence for the out-of-phase component of susceptibility,although it does not even show field-induced SMM behaviour above 2 K.Ab initio calculations were performed in order to shed light on the magnetic dynamics of the complexes,and these studies support the experimental magnetic results.
基金supported by the National Natural Science Foundation of China(No.21271052 and 21905062)the Science and Technology Program Foundation of Guangdong Province(No.2015A030313502)the First talent cultivation program of Guangzhou University(RP2020084).
文摘The electronic[Xe]4f^(13) configurations of Yb(Ⅲ)ions generate a variety of electronic energy levels,resulting in the fantastic optical and magnetic multifunctional properties of Yb(Ⅲ)complexes.Here,2-hydroxy-3-methoxy benzoic acid(H_(2)MBA)was used to construct two dinuclear and one-dimensional Yb(Ⅲ)complexes namely[Yb_(2)(HMBA)_(2)(MBA)_(2)(DMF)_(2)(H_(2)O)_(2)]·6H_(2)O(1,DMF=N,N-dimethylformamide)and[NH_(4)][Yb(HMBA)_(4)](2).Fluorescence measurements reveal that H_(2)MBA can sensitize the characteristic near-infrared luminescence of Yb(Ⅲ).Magnetic susceptibility measurements show that the two Yb(Ⅲ)complexes are field-induced single-molecule magnets(SMMs)with anisotropy barriers of 18(1)cm^(-1) and 20(1)cm^(-1) for 1 and 2,respectively.The magnetism-luminescence-structure correlations as well as relaxation pathways are investigated by ab initio calculations and fluorescence spectrometry.
基金The project was supported by the National Natural Science Foundation of China (20471008) and the Fundamental Research Foundation of Beijing Institute of Technology (BIT-UBF-200302B01&BIT-UBF-200502B4221)
文摘A dinuclear complex Cd2（dnba）4（pyridine）4 （dnba = 3,5-dinitrobenzoate） has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, DSC and TG-DTG techniques. The complex with empirical formula C48H32Cd2NI2024 （Mr = 692.83） crystallizes in monoclinic, space group P21/n with a - 12.0344（14）, b = 10.5752（13）, c = 21.578（3） A, β = 104.150（2）°, V = 2662.8（6） A^3, Z = 2, D, = 1.728 g/cm^3,μ（MoKa） = 0.897 mm^-1, F（000） = 1384, S = 1.016 and （△/σ）max = 0.001. R = 0.0638 and wR = 0.0737 for all data; the final R = 0.0337 and wR = 0.0644. In this complex, four carboxylates are bidentate-or chelate-coordinated with the Cd（Ⅱ） centers to give the dinuclear structure. The other coordination positions of Cd（Ⅱ） are occupied by the lone pair electrons from N of four pyridines. Thermal analyses DSC and TG-DTG have been used to determine the thermal decomposition mechanism of the title complex.
基金financially supported by the National Natural Science Foundation of China (Nos. 21374123 and U1362204)
文摘5,6,7-Trihydroquinolin-8-one was condensed with the corresponding benzidine to give N,N′-bis（5,6,7-trihydroquinolin-8-ylidene）-[1,1′-biphenyl]-4,4′-diamine derivatives（L1–L3）. The ligands were reacted with two equivalents of Ni Cl2·6H2O in a mixture of Et OH and CH2Cl2 to afford the corresponding dinickel（II） chloride complexes（Ni1-Ni3）. The organic compounds were completely characterized, whilst the bi-metallic complexes were characterized by FTIR spectra and elemental analysis. These nickel complexes exhibited high activities towards ethylene polymerization in the presence of either MAO or Me2AlCl, maintaining a high activity over a prolonged period. The obtained polyethylenes were confirmed as having low molecular weights by GPC analysis.
文摘The title compound was synthesized by the solid-state reaction of (NH_4)_6Mo_7O_(24)·4H_2O, Na_2C_2O_4, NH_2OH·HCl and Bu_4NBr at 90 ℃ for 10 h and crystallized from acetone-ether. The green crystal belongs to the monoclinic space group P2_1/n with a=9. 908(2), b= 17, 873(2), c= 13/450(2) A , β= 90. 09(1 )°,V = 2381. 6 (7 ) A￣3 , D_c = 1. 359 g/cm￣3 , Z= 2. The structure was refined to R =0. 0427 for 2562 reflections. The anion of the title compound can be described as an oxalate ligand (C_2O4￣2 ) bridging two [MoCl_2O(OH)] units, which contain Mo(V)atoms.
基金Supported by the Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)Science and Technology Committee of Hengyang(2013KG77)the Construct Program of the Key Discipline in Hunan Province
文摘A new dinuclear manganese complex [Mn2（L）2（2,2＇-bipy）2（H2O）512·3H2O has been synthesized with MnSO4·H2O, 2,2＇-bibenzoic acid （H2L） and 2,2＇-bipyridine（2,2＇-bipy） in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group Pi with a = 9.9944（10）, b = 21.939（2）, c = 25.628（3） A, a = 108.429（3）, β = 100.613（4）, 7 = 102.821（3）°, V = 4997.9（9） A3, Dc= 1.355 g/cm^3, Z = 2, F（000） = 2108, GOOF = 1.074, the R= 0.0626 and wR= 0.1531. The structure of the complex contains two [Mn2（L）2（2,2＇-bipy）2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.
基金supported by the Science and Technology Bureau of Jinhua City (No. 2003-01-179)
文摘A new 4-chlorobenzoic acid bridge Co（Ⅱ ） complex [[Co2（2,2＇-bpy）2（μ-L）e（L）2（μ-H2O）] （HL = 4-chlorobenzoic acid） has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537（5）, b = 16.212（3）, c = 15.306（3） A, β= 124.37（3）°, V= 4616.1（16）A3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, p = 1.012 mm-1, F（000） = 2176, the final R = 0.0338 and wR= 0.0810. The title complex is composed of dinuclear [Co2（2,2＇-bpy）2（μ-L）2（L）2（μ-HaO）] molecules. Each Co（Ⅱ ） atom is coordinated by two nitrogen atoms from one 2,2’-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co（Ⅱ） atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.
基金supported by the National Natural Science Foundation of China (No. 20972124)the China Postdoctoral Science Foundation (No. 20080441180)the Natural Science Foundation of Shaanxi Province (No. 2007B04)
文摘A new ligand 2-（4,5-dihydro-2-thiazolyl）-6-methoxyl benzothiazole and its new dinuclear Co（II） coordination complex [Co（C11H10N2OS2）Cl2]2·2CHCl3 （1） have been synthesized and characterized. Complex 1 was synthesized by the reaction of Co（II） salt with 2-（4,5-dihydro- 2-thiazolyl）-6-methoxyl benzothiazole under room-temperature evaporation condition and struc- turally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The supramolecular network of complex 1 is stabilized by the presence of intermolecular interaction, such as C-H···Cl hydrogen bonding and π-π stacking. The complex crystallizes in triclinic, space group P1 with a = 8.3288（12）, b = 10.5273（15）, c = 10.822（2）, α = 93.416（3）, β = 90.864（3）, γ = 94.890（3）o, V = 943.60（2）3, Z = 2, Dc = 1.758 g/cm3, F（000） = 498 and μ = 1.840 mm-1. The final complex [Co（C11H10N2OS2）Cl2]2·2CHCl3 is a diplex bridged dinuclear complex consisting of two Co（II） ions, two ligands, two bridging Cl- anions and two terminal Cl- anions.
基金financially supported by the National Key R&D Program of China (No. 2021YFA1501700)the National Natural Science Foundation of China+1 种基金Basic Science Center Program (No.51988102)the National Natural Science Foundation of China (No. 52073272)
文摘Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.
基金the Natural Science Foundation of Shandong Province(No.Y2 0 0 2 B0 6 )
文摘A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.
