A series of isomeric sandwich-type dysprosiacarboranyl complexes,including[Na(THF)_(5)][3.2'-(THF)_(2)-3.2-Dy(1,2-C_(2)B_(9)H_(11))_(x)(1'7'-C_(2)B_(9)H_(11))_(2-x))(o/m-Dy)and[Na(THF)_(5)][2.2'-(THF)_...A series of isomeric sandwich-type dysprosiacarboranyl complexes,including[Na(THF)_(5)][3.2'-(THF)_(2)-3.2-Dy(1,2-C_(2)B_(9)H_(11))_(x)(1'7'-C_(2)B_(9)H_(11))_(2-x))(o/m-Dy)and[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,7-C_(2)B_(9)H_(11))2](m-Dy)were synthesized by using the isomeric dicarbollide ligands,namely[nido-7,8-C2BgH_(11)]^(2-)and[nido-7,9-C_(2)B_(9)H_(11)]^(2-).The structural details of o/m-Dy and m-Dy and magnetic dynamics of m-Dy were investigated to compare with the previous study on[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,2-C_(2)B_(9)H_(11))_(2)]o-Dy.The bending angles of sandwiched dysprosiacarboranes are straightened so as to improve energy bar-riers(U_(eff))from 430(5)to 591(0)K.Magneto-structural correlations show that the introduction of meta-C sites within the π-electron delocalized heterocyclic ring can effectively shorten the Dy-C_(2)B_(3)centroid distance and increase the C_(2)B_(3)centroid...Dy...C_(2)B_(3)centroid bending angle which is attributed to the dif-ferences in electronegativity between C and B atoms on the ring of C_(2)B_(3)^(2-).Therefore,to further enhance the performance of single-molecule magnets(SMMs)on this basis,future endeavors should focus on diminishing the equatorial solvent molecules to make a wider C2B3...Dy...C_(2)B_(3)bending angle.展开更多
基金the National Natural Science Foundation of China(22375157)the Programme of Introducing Talents of Discipline to Universities(B23025)+4 种基金State Key Laboratory of Electrical Insulation and Power Equipment(EIPE23402,EIPE23405)SpecialSupportPlanof ShaanxiProvincefor Young Top-notch Talent,the Fundamental Research Funds for Central Universities(xtr052023002,xzy012023024)the China Postdoctoral Science Foundation(2023M742783)Shaanxi Postdoctoral Science Foundation(2023BSHYDZZ12)the"Scientists+engineers"Team Building Project of Qin Chuang Yuan(2022KXJ-088).
文摘A series of isomeric sandwich-type dysprosiacarboranyl complexes,including[Na(THF)_(5)][3.2'-(THF)_(2)-3.2-Dy(1,2-C_(2)B_(9)H_(11))_(x)(1'7'-C_(2)B_(9)H_(11))_(2-x))(o/m-Dy)and[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,7-C_(2)B_(9)H_(11))2](m-Dy)were synthesized by using the isomeric dicarbollide ligands,namely[nido-7,8-C2BgH_(11)]^(2-)and[nido-7,9-C_(2)B_(9)H_(11)]^(2-).The structural details of o/m-Dy and m-Dy and magnetic dynamics of m-Dy were investigated to compare with the previous study on[Na(THF)_(5)][2.2'-(THF)_(2)-2.2'-Dy(1,2-C_(2)B_(9)H_(11))_(2)]o-Dy.The bending angles of sandwiched dysprosiacarboranes are straightened so as to improve energy bar-riers(U_(eff))from 430(5)to 591(0)K.Magneto-structural correlations show that the introduction of meta-C sites within the π-electron delocalized heterocyclic ring can effectively shorten the Dy-C_(2)B_(3)centroid distance and increase the C_(2)B_(3)centroid...Dy...C_(2)B_(3)centroid bending angle which is attributed to the dif-ferences in electronegativity between C and B atoms on the ring of C_(2)B_(3)^(2-).Therefore,to further enhance the performance of single-molecule magnets(SMMs)on this basis,future endeavors should focus on diminishing the equatorial solvent molecules to make a wider C2B3...Dy...C_(2)B_(3)bending angle.
