A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2（hmp）4（N3）4（O2CR）2]（hmp-is the anion of...A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2（hmp）4（N3）4（O2CR）2]（hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate）crystallizes in the monoclinic system,space group P21/c with a = 10.519（5）,b = 22.109（10）,c = 23.235（9）,β = 106.096（17）o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192（4）3,Dc = 1.533 g/cm3,F（000）= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I 2σ（I）.X-ray diffraction analysis reveals that each Mn（III）center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni（II）is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.展开更多
A tetranuclear cubane-type complex[Co_(4)(ntfa)_(4)(CH_(3)O)_(4)(CH_(3)OH)_(4)](1)with a{Co_(4)O_(4)}core,and a mononuclear complex[Co(ntfa)_(2)(CH_(3)OH)_(2)](2)have been rationally obtained by adjusting the ratio of...A tetranuclear cubane-type complex[Co_(4)(ntfa)_(4)(CH_(3)O)_(4)(CH_(3)OH)_(4)](1)with a{Co_(4)O_(4)}core,and a mononuclear complex[Co(ntfa)_(2)(CH_(3)OH)_(2)](2)have been rationally obtained by adjusting the ratio of theβ-diketonate and Co(II)ions,with the synthetic processes being monitored by in situ microcalorimetry.Then,following synthetic conditions to obtain 2,but using three distinct N-donor coligands-2,2’-bipyridyl(bpy),6,6’-dimethyl-2,2’-bipyridyl(6,6-(CH_(3))_(2)-bpy)and 5,5’-dimethyl-2,2’-bipyridyl(5,5-(CH_(3))_(2)-bpy)-three novel mononuclear complexes have been obtained,[Co(ntfa)_(2)(bpy)_(2)](3),[Co(ntfa)_(2)(6,6-(CH_(3))_(2)-bpy)_(2)](4)and[Co(ntfa)_(2)(5,5-(CH_(3))_(2)-bpy)_(2)](5).The introduction of different capping coligands-as singlecrystal X-ray crystallography ascertains-fine-tunes the structures,with changes in both the distortion degree of the coordination geometry and the intermolecular interactions,which have a direct impact on the magnetic properties of these complexes.Magnetic investigations reveal field-induced single-ion magnet behavior in all complexes with distinct energy barriers(Ueff)-39.06(1),36.65(2),36.32(3),28.26(4)and 15.85 K(5).Magnetic experiments together with HF-EPR measurements and theoretical calculations demonstrate that 2 features easy-axis magnetic anisotropy(D=-60.48 cm^(-1)),whereas 3-5 show easy-plane magnetic anisotropies-D=+70.77 cm^(-1) for 3,+35.71 cm^(-1) for 4,and+51.28 cm^(-1) for 5.To our knowledge,such reversal of anisotropic nature driven by coligands is unprecedented.展开更多
基金Financially supported by the National Natural Science Foundation of China (No.20971063)
文摘A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2（hmp）4（N3）4（O2CR）2]（hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate）crystallizes in the monoclinic system,space group P21/c with a = 10.519（5）,b = 22.109（10）,c = 23.235（9）,β = 106.096（17）o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192（4）3,Dc = 1.533 g/cm3,F（000）= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I 2σ（I）.X-ray diffraction analysis reveals that each Mn（III）center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni（II）is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.
基金support from the National Natural Science Foundation of China(21863009,U20A2073)the Natural Science Foundation of Ningxia Province(2020AAC02005)+5 种基金the Discipline Project of Ningxia(NXYLXK2017A04)the Guizhou Education Department Youth Science and Technology Talents Growth Project(No.KY[2020]158)the 2019 Post-doctoral Junior Leader-Retaining Fellowship,la Caixa Foundation(ID100010434 and fellowship code LCF/BQ/PR19/11700011)the“Generalitat Valenciana”(SEJI/2020/034)the“Ramón y Cajal”program(J.F.-S.)support from the European Research Council under the European Union’s Horizon 2020 research and innovation programme/ERC Grant Agreement No.814804,MOF-reactors.
文摘A tetranuclear cubane-type complex[Co_(4)(ntfa)_(4)(CH_(3)O)_(4)(CH_(3)OH)_(4)](1)with a{Co_(4)O_(4)}core,and a mononuclear complex[Co(ntfa)_(2)(CH_(3)OH)_(2)](2)have been rationally obtained by adjusting the ratio of theβ-diketonate and Co(II)ions,with the synthetic processes being monitored by in situ microcalorimetry.Then,following synthetic conditions to obtain 2,but using three distinct N-donor coligands-2,2’-bipyridyl(bpy),6,6’-dimethyl-2,2’-bipyridyl(6,6-(CH_(3))_(2)-bpy)and 5,5’-dimethyl-2,2’-bipyridyl(5,5-(CH_(3))_(2)-bpy)-three novel mononuclear complexes have been obtained,[Co(ntfa)_(2)(bpy)_(2)](3),[Co(ntfa)_(2)(6,6-(CH_(3))_(2)-bpy)_(2)](4)and[Co(ntfa)_(2)(5,5-(CH_(3))_(2)-bpy)_(2)](5).The introduction of different capping coligands-as singlecrystal X-ray crystallography ascertains-fine-tunes the structures,with changes in both the distortion degree of the coordination geometry and the intermolecular interactions,which have a direct impact on the magnetic properties of these complexes.Magnetic investigations reveal field-induced single-ion magnet behavior in all complexes with distinct energy barriers(Ueff)-39.06(1),36.65(2),36.32(3),28.26(4)and 15.85 K(5).Magnetic experiments together with HF-EPR measurements and theoretical calculations demonstrate that 2 features easy-axis magnetic anisotropy(D=-60.48 cm^(-1)),whereas 3-5 show easy-plane magnetic anisotropies-D=+70.77 cm^(-1) for 3,+35.71 cm^(-1) for 4,and+51.28 cm^(-1) for 5.To our knowledge,such reversal of anisotropic nature driven by coligands is unprecedented.
