Consequences of Amide Connectivity in the Supramolecular Polymerization of Porphyrins: Spectroscopic Observations Rationalized by Theoretical Modelling,Chemistry - A European Journal

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Consequences of Amide Connectivity in the Supramolecular Polymerization of Porphyrins: Spectroscopic Observations Rationalized by Theoretical Modelling
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2021-05-02 , DOI: 10.1002/chem.202101036
Elisabeth Weyandt _{1,

2} , Ivo A W Filot _{2,

3} , Ghislaine Vantomme _{1,

2} , E W Meijer _{1,

2}

Affiliation

The correlation between molecular structure and mechanism of supramolecular polymerizations is a topic of great interest, with a special focus on the pathway complexity of porphyrin assemblies. Their cooperative polymerization typically yields highly ordered, long 1D polymers and is driven by a combination of π-stacking due to solvophobic effects and hydrogen bonding interactions. Subtle changes in molecular structure, however, have significant influence on the cooperativity factor and yield different aggregate types (J- versus H-aggregates) of different lengths. In this study, the influence of amide connectivity on the self-assembly behavior of porphyrin-based supramolecular monomers was investigated. While in nonpolar solvents, C=O centered monomers readily assemble into helical supramolecular polymers via a cooperative mechanism, their NH centered counterparts form short, non-helical J-type aggregates via an isodesmic pathway. A combination of spectroscopy and density functional theory modelling sheds light on the molecular origins causing this stunning difference in assembly properties and demonstrates the importance of molecular connectivity in the design of supramolecular systems. Finally, their mutual interference in copolymerization experiments is presented.

中文翻译：

卟啉超分子聚合中酰胺连接的后果：通过理论模型合理化光谱观察

超分子聚合的分子结构和机理之间的相关性是一个非常有趣的话题，特别关注卟啉组装体的途径复杂性。它们的协同聚合通常产生高度有序的长一维聚合物，并且由疏溶剂效应和氢键相互作用引起的 π 堆积组合驱动。然而，分子结构的细微变化对协同因子有显着影响，并产生不同长度的不同聚集体类型（J-与H-聚集体）。在本研究中，研究了酰胺连接性对卟啉基超分子单体自组装行为的影响。在非极性溶剂中，以 C=O 为中心的单体很容易通过协作机制组装成螺旋超分子聚合物，而以 NH 为中心的对应物则通过等线途径形成短的非螺旋 J 型聚集体。光谱学和密度泛函理论建模的结合揭示了导致组装特性惊人差异的分子起源，并证明了分子连接性在超分子系统设计中的重要性。最后，介绍了它们在共聚实验中的相互干扰。

更新日期：2021-07-02

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