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首页> 外文期刊>Chemistry: A European journal >Realization of Unusual Ligand Binding Motifs in Metalated Container Molecules: Synthesis, Structures, and Magnetic Properties of the Complexes [(L~(Me))Ni_2(mu-L')]~(n+) with L' =NO_3 ~-, NO_2~- , N_3~-, N_2H_4, Pyridazine, Phthalazine, Pyrazolate, a
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Realization of Unusual Ligand Binding Motifs in Metalated Container Molecules: Synthesis, Structures, and Magnetic Properties of the Complexes [(L~(Me))Ni_2(mu-L')]~(n+) with L' =NO_3 ~-, NO_2~- , N_3~-, N_2H_4, Pyridazine, Phthalazine, Pyrazolate, a

机译：金属容器分子中异常配体结合基序的实现：[[L〜（Me））Ni_2（mu-L'）]〜（n +）L'= NO_3〜-，NO_2的配合物的合成，结构和磁性〜-，N_3〜-，N_2H_4，哒嗪，酞嗪，吡唑啉，a

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A series of dinickel(II) complexes with the 24-membered macrocyclic hexaazadithiophenol ligand H_2L~(Me) was prepared and examined. The doubly deprotonated form (L~(Me))~(2-) forms complexes of the type [(L~(Me))Ni_2~(II)(mu-L')]~(n+) with a bioctahedral N_3Ni~(II)(mu-SR)_2(mu-L')Ni~(II)N_3 core and an overall calixarene-like structure. The bridging coordination site L' is accessible for a wide range of exogenous coligands. In this study L' = NO_3 , NO_2~-, N_3~-, N_2H_4, pyrazolate (pz), pyridazine (pydz), phthalazine (phtz), and benzoate (OBz). Crystallographic studies reveal that each substrate binds in a distinct fashion to the [(L~(Me))Ni_2]~(2+) portion: NO_2 , N_2H_4, pz, pydz, and phtz form mu_(1,2)-bridges, whereas NO_3~-, N_3~-,and OBz~- are mu_(1.3)-bridging. These distinctive binding motifs and the fact that some of the coligands adopt unusual conformations is discussed in terms of complementary host-guest interactions and the size and form of the binding pocket of the [(L~(Me))Ni_2]~(2+) fragment. UV/Vis and electrochemical studies reveal that the solid-state structures are retained in the solution state. The relative stabilities of the complexes indicate that the [(L~(Me))Ni_2]~(2+) fragment binds anionic coligands preferentially over neutral ones and strongfield ligands over weak-field ligands. Secondary van der Waals interactions also contribute to the stability of the complexes. Intramolecular ferromagnetic exchange interactions are present in the nitrite-, pyridazine-, and the benzoato-bridged complexes where J=+6.7,+3.5, and +5.8 cm~(-1) (H= -2JS_1S_2, S_1 = S2 = 1) as indicated by magnetic susceptibility data taken from 300 to 2K. In contrast, the azido bridge in [(LMe)Ni2(jnu-N3)]+ results in an antiferromagnetic exchange interaction J= -46.7 cm~(-1). An explanation for this difference is qualitatively discussed in terms of bonding differences.
机译：制备并研究了一系列具有24元大环六氮杂二硫酚配体H_2L〜（Me）的二镍（II）配合物。双质子化形式（L〜（Me））〜（2-）形成[（L〜（Me））Ni_2〜（II）（mu-L'）]〜（n +）型与生物体面N_3Ni〜 （II）（mu-SR）_2（mu-L'）Ni〜（II）N_3核和整体杯状芳烃样结构。桥接协调位点L'可用于多种外源大肠菌素。在这项研究中，L'= NO_3，NO_2〜-，N_3〜-，N_2H_4，吡唑酯（pz），哒嗪（pydz），酞嗪（phtz）和苯甲酸酯（OBz）。晶体学研究表明，每种底物均以独特的方式与[（L〜（Me））Ni_2]〜（2+）部分结合：NO_2，N_2H_4，pz，pydz和phtz形成mu_（1,2）-桥，而NO_3〜-，N_3〜-和OBz〜-是mu_（1.3）桥。这些互补的结合基序和一些大肠菌群采用不同的构象这一事实，是通过互补的宿主-客体相互作用以及[（L〜（Me））Ni_2]〜（2+ ）片段。 UV / Vis和电化学研究表明，固态结构以溶液状态保留。配合物的相对稳定性表明，[（L〜（Me））Ni_2]〜（2+）片段优先结合阴离子大分子，而不是中性大分子，强场配体优先于弱场配体。二级范德华相互作用也有助于配合物的稳定性。分子内铁磁性交换相互作用存在于亚硝酸盐，哒嗪和苯并氨基桥连的络合物中，其中J = + 6.7，+ 3.5和+5.8 cm〜（-1）（H = -2JS_1S_2，S_1 = S2 = 1）如从300到2K的磁化率数据所示。相反，[（LMe）Ni2（jnu-N3）] +中的叠氮基桥导致反铁磁交换相互作用J = -46.7 cm〜（-1）。关于这种差异的解释将根据键合差异进行定性讨论。

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