Unique Dimerization Topology and Countercation Binding Modes in 12‐Metallacrown‐4 Compounds
Unique Dimerization Topology and Countercation Binding Modes in 12‐Metallacrown‐4 Compounds
复制标题
DOI：
10.1002/ejic.202200439
复制
发表时间：
2022-09
影响因子：
2.3
通讯作者：
Elvin V. Salerno;Collin M. Foley;Vittoria Marzaroli;Bernadette L. Schneider;Max D. Sharin;J. Kampf;L. Marchiò;M. Zeller;R. Guillot;T. Mallah;M. Tegoni;V. Pecoraro;C. Zaleski
中科院分区：
文献类型：
--
作者：
Elvin V. Salerno;Collin M. Foley;Vittoria Marzaroli;Bernadette L. Schneider;Max D. Sharin;J. Kampf;L. Marchiò;M. Zeller;R. Guillot;T. Mallah;M. Tegoni;V. Pecoraro;C. Zaleski
合成了七种基于Ln[12‐MCM(III)N（shi）‐4]的二聚体金属冕（MC），其中LnIII=Dy, Ho， Yb或Y， MIII=Mn或Ga， shi3−为水杨酸盐，用单晶X射线衍射对其进行了表征，并对镝‐锰二聚体的磁性进行了测量。在每个二聚体中，两个Ln[12‐MCM(III)N（shi）‐4]单元由四个桥接的二羧酸阴离子（二苯二甲酸酯、三苯二甲酸酯、二烟酸酯或2,2′‐二硫代二苯甲酸酯）连接。三种不同的对位剂（钠、镓（III）或吡啶）被用来维持二聚体的电荷平衡。虽然吡啶不与二聚体结合，但二羧酸盐的选择决定了Na+或gai2的对偶作用。对于二苯二甲酸盐和三苯三甲酸盐，钠离子结合到与LnIII相反的中央MC腔，对于二烟酸盐，钠离子或镓（III）离子结合到二烟酸盐的吡啶基氮上。所有三种dy2mn8二聚体都表现出相外磁化率信号，这与磁化弛豫的浅势垒一致。
Seven dimeric metallacrowns (MC) based on Ln[12‐MCM(III)N(shi)‐4], where LnIII=Dy, Ho, Yb, or Y, MIII=Mn or Ga, and shi3−is salicylhydroximate, have been synthesized and characterized by single‐crystal X‐ray diffraction, and for the dysprosium‐manganese dimers, the magnetic properties have been measured. In each dimer two Ln[12‐MCM(III)N(shi)‐4] units are linked by four bridging dicarboxylate anions (isophthalate, trimesate, dinicotinate, or 2,2′‐dithiodibenzoate). Three different countercations (sodium, gallium(III), or pyridinium) were used to maintain charge balance of the dimer. While pyridinium does not bind to the dimer, the choice of the dicarboxylate dictates where the countercations Na+or GaIIIbind. With isophthalate and trimesate, the sodium ion binds to the central MC cavity opposite of the LnIII, and with dinicotinate the sodium or gallium(III) ions bind to the pyridyl nitrogen of the dinicotinate. All three Dy2Mn8dimers exhibit an out‐of‐phase magnetic susceptibility signal consistent with a shallow barrier to magnetization relaxation.