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
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.
