Design and Applications of Helical Crystal Spaces by Spontaneous Resolution

手性马鞍形卟啉与4-溴山竹酸形成的氢键络合物发生了自发拆分。2-甲基丁酸乙酯作为手性溶剂用于结晶，对映体过量为50%时，对映体选择性地被包含在晶体的螺旋空间内。在具有相同对映体选择性和对映体过量的蒸气条件下，也观察到了2-甲基丁酸乙酯的包合。为了设计新颖的手性空间和反应场，从吡啶连接的马鞍状卟啉和钯或铂的配合物中制备了新的卟啉二聚体和柱状组合物，通过CSI-MS测量部分检测到了它们。这些超分子组装体与光学活性的穿心莲甲酸相互作用时，CD活性增强，这表明手性信息通过刚性连接物转移到邻近的马鞍型卟啉。

Spontaneous resolution was found to occur for hydrogen-bonded complexes between chiral saddle-shaped porphyrins and 4-Br manderic acid. Ethyl 2-methylbutyrate, which was used as a chiral solvent for the crystallization, was enantioselectively included within helical spaces of the crystals with 50% enantiomeric excess. The inclusion of ethyl 2-methylbutyrate was also observed under vapor conditions with the same enantioselectivity and enantiomeric excess.Novel porphyrin dimer and columnar assemblies, which were partially detected by CSI-MS measurements, were prepared from pyridine-attached saddle-shaped porphyrins and palladium or platinum complexes, in order to design novel chiral spaces and reaction fields. These supramolecular assemblies show enhanced CD activity upon interaction with optically active manderic acid compared with monomenc reference, suggesting that the chiral informations of porphyrin/manderic acid complexes transfer to the neighboring saddle prphyrins via rigid linkers.