Nature of C60 and C70 fullerene encapsulation in a porphyrin‐ and metalloporphyrin‐based cage: Insights from dispersion‐corrected density functional theory calculations,International Journal of Quantum Chemistry

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Nature of C60 and C70 fullerene encapsulation in a porphyrin‐ and metalloporphyrin‐based cage: Insights from dispersion‐corrected density functional theory calculations
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2019-10-29 , DOI: 10.1002/qua.26080
Johanna Camacho Gonzalez ₁ , Sukanta Mondal ₂ , Fernanda Ocayo ₃ , Raul Guajardo‐Maturana ₄ , Alvaro Muñoz‐Castro ₅

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The search for efficient synthetic hosts able to encapsulate fullerenes has attracted attention with regard to the purification and formation of ordered supramolecular architectures. This study of a porphyrin‐based cage as an extension of the well‐described ExCage⁶⁺ and BlueCage⁶⁺, involving viologen as sidearms, provides an interesting scenario where the oblate C₇₀ fullerene is preferred in comparison to the spherical C₆₀. Our results expose the nature of the fullerene‐cage interaction involving ∼50% of dispersion‐type interactions evidencing the strong π⋯π surface stacking, with a complementary contribution by the electrostatic and orbital polarization character produced by a charge reorganization with a charge accumulation facing the porphyrin macrocycles and a charge depletion along the equator formed by the viologens sidearms. Interestingly, the central N₄H₂ ring from each porphyrin contributes to the dispersion term via N‐H⋯π interactions, which is decreased when the metallate N₄Zn is evaluated. Thus, the formation of stable and selective fullerene encapsulation can be achieved by taking into account two main driving forces, namely, (a) the extension of the π⋯π and X‐H⋯π stacking surface and (b) charge reorganization over the fullerene surfaces, which can be used to control fine tuning of the encapsulation thanks to the introduction of more electron‐deficient and electron‐rich groups within the host cage.

中文翻译：

基于卟啉和金属卟啉的笼中C60和C70富勒烯封装的性质：色散校正密度泛函理论计算的见解

在有序超分子结构的纯化和形成方面，寻找能够包封富勒烯的有效合成主体引起了人们的注意。这项基于卟啉的笼子作为完善描述的ExCage ⁶⁺和BlueCage ⁶⁺的扩展的研究，涉及紫精作为侧臂，提供了一个有趣的场景，与球形C ₆₀相比，扁球形C ₇₀富勒烯更可取。我们的研究结果揭示了富勒烯-笼相互作用的性质，涉及约50％的分散型相互作用，表现出很强的π⋯π表面堆叠，并且由于电荷重组而产生的静电和轨道极化特性产生了互补作用紫卟啉大环和紫罗兰侧臂形成的赤道沿线的电荷耗尽。有趣的是，每个卟啉的中心N ₄ H ₂环通过N-H⋯π相互作用而有助于分散项，当金属化物N ₄评估锌。因此，可以通过考虑两个主要驱动力来实现稳定和选择性富勒烯封装的形成，即，（a）π⋯π和X-H⋯π堆积表面的扩展，以及（b）在富勒烯表面，由于在宿主笼子中引入了更多的缺电子和富电子基团，因此可用于控制封装的微调。

更新日期：2019-12-21

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