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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Self-assembly of porphyrin hexamers via bidentate metal-ligand coordination
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Self-assembly of porphyrin hexamers via bidentate metal-ligand coordination

机译：通过双齿金属配体协调自组装卟啉六辐射器

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摘要

The supramolecular assembly of metal-porphyrin hexamers with bidentate ligands in chloroform solutions is demonstrated by UV/Vis and H-1 NMR-titrations, and Small Angle Neutron Scattering (SANS) experiments. Titrations of zinc porphyrin hexamer Zn1 with 1,4-diazabicyclo[2,2,2]octane (DABCO) revealed that at a DABCO/Zn1 molar ratio of 3, intermolecular sandwich complexes are formed, which can be considered as circular-shaped porphyrin ladders. These supramolecular complexes further aggregate into larger polymeric stacks, as a result of a combination of cooperativity effects, - stacking interactions, and chelate effects. The presence of rodlike assemblies in solution, formed by assembly of Zn1 and DABCO, is confirmed by SANS-experiments. Using a model for cylindrical assemblies, curve fitting calculations reveal that rods with an average length of 26 nm and a radius of 30-35 angstrom were formed, corresponding to columnar stacks of approximately 30 hexamer molecules. In contrast, the metal-free hexamer H(2)1 did not form extended assemblies due to the absence of coordinative intermolecular interactions.
机译：通过UV / Vis和H-1 NMR滴定和小角度中子散射（SAN）实验，证明了氯仿溶液中具有二齿配体的金属 - 卟啉六烷烃的超分子组装，以及小角度中子散射（SAN）实验。用1,4-二氮杂双环[2,2,2]辛烷值（DABCO）的锌卟啉六烷烃Zn1的滴定显示，在Dabco / Zn1摩尔比为3，形成分子间夹心复合物，其可被认为是圆形卟啉梯子。这些超分子复合物进一步聚集成较大的聚合物堆叠，其结果是合作效应，堆叠相互作用和螯合作用的组合。通过组装Zn1和Dabco组装的溶液中存在棒状组件的存在，通过SAN-DIPININIMING证实。使用圆柱组件的模型，形成平均长度为26nm和半径为30-35埃的杆，对应于约30六聚合物分子的柱状堆。相反，由于没有协调的分子间相互作用，无金属六甲醇H（2）1没有形成延长的组件。

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