Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing , Beijing 100083, China.
J Org Chem. 2013 Oct 4;78(19):9949-55. doi: 10.1021/jo401825k. Epub 2013 Sep 24.
A C1-symmerical meso-substituted ABCD-type porphyrin, [5-phenyl-10-(2-hydroxynaphthyl)-15-(4-hydroxyphenyl)porphyrinato]zinc(II) (1), has been synthesized and characterized. The molecular structure of 1 has been determined by single-crystal X-ray diffraction analysis. The complex 1 crystallizes in a triclinic system with one pair of enantiomeric molecules per unit cell. Resolution of the racemic mixture has been achieved by chiral HPLC techniques. In particular, the absolute configurations of the enantiomers have been assigned from NMR spectroscopic analysis with L-Phe-OMe as the chiral solvating agent (CSA). The assignments have also been unambiguously confirmed by single-crystal X-ray diffraction analysis. The present results suggest that the CSA-NMR anisotropy strategy is applicable for the stereochemistry determination of chiral host-guest complexes with multiple intermolecular interactions. In addition, the multiple intermolecular interactions between the enantiomerically pure porphyrin S-1 and L-Phe-OMe are proved in the solid state by single-crystal X-ray diffraction analysis.
一种 C1-对称的介孔 ABCD 型卟啉，[5-苯基-10-(2-羟基萘基)-15-(4-羟基苯基)卟啉基]锌(II)（1），已经被合成并进行了表征。通过单晶 X 射线衍射分析确定了 1 的分子结构。该配合物 1 结晶在一个具有每单位细胞一对对映体分子的三斜晶系中。通过手性 HPLC 技术实现了外消旋混合物的拆分。特别是，通过使用 L-苯丙氨酸甲酯作为手性溶剂（CSA）的 NMR 光谱分析确定了对映体的绝对构型。这些分配也通过单晶 X 射线衍射分析得到了明确的证实。目前的结果表明，CSA-NMR 各向异性策略适用于具有多个分子间相互作用的手性主体-客体配合物的立体化学测定。此外，通过单晶 X 射线衍射分析证明了手性卟啉 S-1 和 L-苯丙氨酸甲酯之间在固态下存在多个分子间相互作用。
