Probing the Role of Glycol Chain Lengths in π-Donor–Acceptor [2]Pseudorotaxanes Based on Monopyrrolo-Tetrathiafulvalene and Cyclobis(paraquat-p-phenylene)

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• 作者：Rikke Kristensen ; Sissel S. Andersen ; Gunnar OlsenJan O. Jeppesen
• 刊名：Journal of Organic Chemistry
• 出版年：2017
• 出版时间：February 3, 2017
• 年：2017
• 卷：82
• 期：3
• 页码：1371-1379
• 全文大小：498K
• ISSN：1520-6904

文摘

We have investigated and quantified the role that the glycol chain length has on the strength of the noncovalent bonding interactions taking place between cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺) and five different monopyrrolo-tetrathiafulvalene (MPTTF) derivatives that only differ in the length of the N-substituted glycol chain. The MPTTF derivatives were used to form [2]pseudorotaxanes by mixing them with CBPQT⁴⁺. The binding constants (K_a) associated with the complexation process leading to the formation of the [2]pseudorotaxanes were obtained using the UV–vis−NIR dilution method and the [2]pseudorotaxanes were characterized structurally using ¹H NMR spectroscopy. These experimental investigations clearly indicate that the glycol chains provide additional stability to the [2]pseudorotaxanes findings that were further supported by density functional theory (DFT) studies. The DFT calculated superstructure of the [2]pseudorotaxane 3⊂CBPQT⁴⁺ reveal that [C–H···O] hydrogen bonding interactions between the acidic α-H protons in CBPQT⁴⁺ and the oxygen atoms present in the glycol chain can take place on the exterior of the [2]pseudorotaxane. However, the length of the glycol chain is of paramount importance and the present studies show that the first and second oxygen atom in the [2]pseudorotaxanes 2–5⊂CBPQT⁴⁺ are engaged in [C–H···O] hydrogen bonding interactions with CBPQT⁴⁺, whereas the third and fourth oxygen atoms are not.