Porphyrin cage-compounds are used as biomimetic models and substrate-selective catalysts in supramolecular chemistry. In this work we present the resolution of planar-chiral porphyrin cages and the determination of their absolute configuration by vibrational circular dichroism in combination with density functional theory calculations. The chiral porphyrin-cages form complexes with achiral and chiral viologen-guests and upon binding one of the axial enantiomorphs of the guest is bound selectively, as is indicated by induced-electronic-dichroism-spectra in combination with calculations. This host-guest binding also leads to unusual enhanced vibrational circular dichroism, which is the result of a combination of phenomena, such as rigidification of the host and guest structures, charge transfer, and coupling of specific vibration modes of the host and guest. The results offer insights in how the porphyrin cage-compounds may be used to construct a future molecular Turing machine that can write chiral information onto polymer chains.

卟啉笼化合物在超分子化学中用作仿生模型和底物选择性催化剂。在这项工作中，我们提出了平面手性卟啉笼的分辨率，并通过振动圆二色性结合密度泛函理论计算确定了它们的绝对构型。手性卟啉笼与非手性和手性紫精客体形成复合物，并且在结合客体的轴向对映体之一时选择性地结合，如诱导电子二色性光谱结合计算所示。这种主客体结合还会导致异常增强的振动圆二色性，这是多种现象组合的结果，例如主体和客体结构的刚性、电荷转移、以及主客体特定振动模式的耦合。结果提供了关于如何使用卟啉笼化合物构建未来分子图灵机的见解，该机可以将手性信息写入聚合物链。