Pavlishchuk Anna V, Kolotilov Sergey V, Zeller Matthias, Lofland Samuel E, Thompson Laurence K, Addison Anthony W, Hunter Allen D
Department of Chemistry, Taras Shevchenko National University of Kyiv , Volodymyrska str. 62, Kiev 01601, Ukraine.
L.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine , Prospect Nauki 31, Kiev 03028, Ukraine.
Inorg Chem. 2017 Nov 6;56(21):13152-13165. doi: 10.1021/acs.inorgchem.7b01944.
Complexes {[LnCu(GlyHA)(m-bdc)(HO)][LnCu(GlyHA)(SO)(m-bdc)(HO)]}·(30 + 2x)HO (where GlyHA = glycinehydroxamate, m-bdc = m-phthalate; Ln = Pr and x = 0.21 for compound 1, or Ln = Sm and x = 0.24 for 3) and one-dimensional (1D) coordination polymers {[NdCu(GlyHA)(HO)(m-bdc)]n[NdCu(GlyHA)(HO)(μ-CO)(m-bdc)]}·13nHO (2) and {EuCu(GlyHA)(HO)[EuCu(GlyHA)(m-bdc)(HO)]}·17nHO (4) were obtained starting from the 15-metallacrown-5 complexes {[LnCu(GlyHA)(SO)(HO)]}(SO)·6HO (Ln = Pr, Nd, Sm, Eu) by the partial or complete metathesis of sulfate anions with m-phthalate. Compounds 1 and 3 contain unprecedented quadruple-decker neutral metallacrown assemblies, where the [LnCu(GlyHA)] cations are linked by m-phthalate dianions. In contrast, in complexes 2 and 4, these components assemble into 1D chains of coordination polymers, the adjacent {[NdCu(GlyHA)(HO)(m-bdc)]} 1D chains in 2 being separated by discrete [NdCu(GlyHA)(HO)(μ-CO)(m-bdc)]} complex anions. The crystal lattices of 2 and 4 contain voids filled by solvent molecules. Desolvated 4 is able to absorb up to 0.12 cm/g of methanol vapor or 0.04 cm/g of ethanol at 293 K. The isotherm for methanol absorption by compound 4 is consistent with a possible "gate opening" mechanism upon interaction with this substrate. The χT vs T data for complexes 1-4 and their simpler starting materials {[LnCu(GlyHA)(SO)(HO)]}(SO)·6HO (Ln(III) = Pr, Nd, Sm, Eu) were fitted using an additive model, which takes into account exchange interactions between lanthanide(III) and copper(II) ions in the metallamacrocycles via a molecular field model. The exchange interactions between adjacent Cu(II) ions in metallacrown fragments were found to fall in the range of -47 < J < -63 cm. These complexes are the first examples of a Ln(III)-Cu(II) 15-metallacrowns-5 (Ln(III) = Pr, Nd, Sm, Eu), for which values of exchange parameters have now been reported.
配合物{[LnCu(GlyHA)(间苯二甲酸)(H₂O)][LnCu(GlyHA)(SO₄)(间苯二甲酸)(H₂O)]}·(30 + 2x)H₂O（其中GlyHA = 甘氨酸肟，间苯二甲酸 = 间苯二甲酸根；对于化合物1，Ln = Pr且x = 0.21，或者对于化合物3，Ln = Sm且x = 0.24）以及一维（1D）配位聚合物{[NdCu(GlyHA)(H₂O)(间苯二甲酸)]ₙ[NdCu(GlyHA)(H₂O)(μ - CO)(间苯二甲酸)]}·13nH₂O（2）和{EuCu(GlyHA)(H₂O)[EuCu(GlyHA)(间苯二甲酸)(H₂O)]}·17nH₂O（4）是通过硫酸根阴离子与间苯二甲酸的部分或完全复分解反应，从15 - 金属冠醚 - 5配合物{[LnCu(GlyHA)(SO₄)(H₂O)]}(SO₄)·6H₂O（Ln = Pr、Nd、Sm、Eu）制得的。化合物1和3包含前所未有的四重中性金属冠醚组装体，其中[LnCu(GlyHA)]阳离子通过间苯二甲酸二阴离子相连。相比之下，在配合物2和4中，这些组分组装成一维配位聚合物链，2中相邻的{[NdCu(GlyHA)(H₂O)(间苯二甲酸)]}一维链被离散的[NdCu(GlyHA)(H₂O)(μ - CO)(间苯二甲酸)]}络合阴离子隔开。2和4的晶格包含被溶剂分子填充的空隙。脱溶剂后的4在293 K时能够吸收高达0.12 cm³/g的甲醇蒸汽或0.04 cm³/g的乙醇。化合物4对甲醇的吸收等温线与与该底物相互作用时可能的“门打开”机制一致。使用加和模型对配合物1 - 4及其更简单的起始材料{[LnCu(GlyHA)(SO₄)(H₂O)]}(SO₄)·6H₂O（Ln(III) = Pr、Nd、Sm、Eu）的χT对T数据进行拟合，该模型通过分子场模型考虑了金属大环中镧系(III)和铜(II)离子之间的交换相互作用。发现金属冠醚片段中相邻Cu(II)离子之间的交换相互作用在 - 47 < J < - 63 cm⁻¹范围内。这些配合物是首次报道交换参数值的Ln(III) - Cu(II) 15 - 金属冠醚 - 5（Ln(III) = Pr、Nd、Sm、Eu）的例子。
