Over the past few decades,various types of metal-sandwich structures have been synthesized and reported,which significantly advanced organometallic chemistry and contributed to numerous applications.However,charge-neu...Over the past few decades,various types of metal-sandwich structures have been synthesized and reported,which significantly advanced organometallic chemistry and contributed to numerous applications.However,charge-neutral rare-earth(Ⅲ)sandwich structure s based on compact aromatic ligands still remained unexplored due to the challenges in their synthesis.Nevertheless,the immense potential of this type of structure in building high-performance single-molecule magnets(SMMs)has compelled us to overcome these synthetic obstacles.Herein,we aimed to isolate such complexes in a general formula of[(Ring1)RE^(Ⅲ)(Ring2)].[(C_(4)B)^(Et4Me2NR)E^(Ⅲ)(Cp^(iPr5))](3-RE,RE=Y,Dy;(C_(4)B)^(Et4Me2N)=1-(N,N-dimethylamino)-2,3,4,5-tetraethylborolyl;CpiPr5=pentaisopropylcyclopentadienyl)were successfully obtained via the salt-metathesis reaction of the precursor[RE^(Ⅲ)(Cp^(iPr5))(BH4)2-(THF)](1-RE,RE=Y,Dy;THF=tetrahydrofuran)and the new aminoborolide ligand[Na_(2)(C_(4)B)^(Ef4Me2N)(THF)_(2)]_(2)(2),which represent the first neutral rare-earth(Ⅲ)-sandwich complexes ligated by compact aromatic ligands.Both complexes 3-RE were characterized by single-crystal X-ray diffraction,elemental analysis,UV-Vis-NIR and FTIR.Diamagnetic 3-Y was studied by NMR spectroscopy.Static and dynamic magnetic properties of 3-Dy were investigated by SQUID magnetometry,showing a high anisotropy barrier of 785(12)cm-1and open hysteresis loops up to 12 K.The bonding of nitrogen to dysprosium(Ⅲ)near the equatorial plane lowers the anisotropy,and a bulkier ligand in the future should be able to avoid this.This work not only demonstrate s that such type of neutral rare-earth(Ⅲ)-sandwich complexe s is totally synthetically feasible,but also paves the way for the development of high-performance SMMs.展开更多
基金supported by the National High-Level Young Talents Programthe National Natural Science Foundation of China(22371031,22131011,21821003)the funding provided by the University of Oulu(Kvantum Institute)。
文摘Over the past few decades,various types of metal-sandwich structures have been synthesized and reported,which significantly advanced organometallic chemistry and contributed to numerous applications.However,charge-neutral rare-earth(Ⅲ)sandwich structure s based on compact aromatic ligands still remained unexplored due to the challenges in their synthesis.Nevertheless,the immense potential of this type of structure in building high-performance single-molecule magnets(SMMs)has compelled us to overcome these synthetic obstacles.Herein,we aimed to isolate such complexes in a general formula of[(Ring1)RE^(Ⅲ)(Ring2)].[(C_(4)B)^(Et4Me2NR)E^(Ⅲ)(Cp^(iPr5))](3-RE,RE=Y,Dy;(C_(4)B)^(Et4Me2N)=1-(N,N-dimethylamino)-2,3,4,5-tetraethylborolyl;CpiPr5=pentaisopropylcyclopentadienyl)were successfully obtained via the salt-metathesis reaction of the precursor[RE^(Ⅲ)(Cp^(iPr5))(BH4)2-(THF)](1-RE,RE=Y,Dy;THF=tetrahydrofuran)and the new aminoborolide ligand[Na_(2)(C_(4)B)^(Ef4Me2N)(THF)_(2)]_(2)(2),which represent the first neutral rare-earth(Ⅲ)-sandwich complexes ligated by compact aromatic ligands.Both complexes 3-RE were characterized by single-crystal X-ray diffraction,elemental analysis,UV-Vis-NIR and FTIR.Diamagnetic 3-Y was studied by NMR spectroscopy.Static and dynamic magnetic properties of 3-Dy were investigated by SQUID magnetometry,showing a high anisotropy barrier of 785(12)cm-1and open hysteresis loops up to 12 K.The bonding of nitrogen to dysprosium(Ⅲ)near the equatorial plane lowers the anisotropy,and a bulkier ligand in the future should be able to avoid this.This work not only demonstrate s that such type of neutral rare-earth(Ⅲ)-sandwich complexe s is totally synthetically feasible,but also paves the way for the development of high-performance SMMs.
