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首页> 外文期刊>Chemistry: A European journal >Quantum Mechanical and Experimental Validation that Cyclobis(paraquat-p-phenylene) Forms a 1:1 Inclusion Complex with Tetrathiafulvalene
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Quantum Mechanical and Experimental Validation that Cyclobis(paraquat-p-phenylene) Forms a 1:1 Inclusion Complex with Tetrathiafulvalene

机译：环双（百草枯-对亚苯基）与四硫富瓦烯形成1：1包合物的量子力学和实验验证

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摘要

The promiscuous encapsulation of -electron-rich guests by the -electron-deficient host, cyclobis(paraquat-p-phenylene) (CBPQT(4+)), involves the formation of 1:1 inclusion complexes. One of the most intensely investigated charge-transfer (CT) bands, assumed to result from inclusion of a guest molecule inside the cavity of CBPQT(4+), is an emerald-green band associated with the complexation of tetrathiafulvalene (TTF) and its derivatives. This interpretation was called into question recently in this journal based on theoretical gas-phase calculations that reinterpreted this CT band in terms of an intermolecular side-on interaction of TTF with one of the bipyridinium (BIPY2+) units of CBPQT(4+), rather than the encapsulation of TTF inside the cavity of CBPQT(4+). We carried out DFT calculations, including solvation, that reveal conclusively that the CT band emerging upon mixing TTF with CBPQT(4+) arises from the formation of a 1:1 inclusion complex. In support of this conclusion, we have performed additional experiments on a [2]rotaxane in which a TTF unit, located in the middle of its short dumbbell, is prevented sterically from interacting with either one of the two BIPY2+ units of a CBPQT(4+) ring residing on a separate [2]rotaxane in a side-on fashion. This [2]rotaxane has similar UV/Vis and (HNMR)-H-1 spectroscopic properties with those of 1:1 inclusion complexes of TTF and its derivatives with CBPQT(4+). The [2]rotaxane exists as an equimolar mixture of cis- and trans-isomers associated with the disubstituted TTF unit in its dumbbell component. Solid-state structures were obtained for both isomers, validating the conclusion that the TTF unit, which gives rise to the CT band, resides inside CBPQT(4+).
机译：-电子缺陷的主体环双（百草枯-对亚苯基）（CBPQT（4+））的-电子富集的客体的混杂封装涉及1：1包合物的形成。假设是由CBPQT（4+）腔内包含客体分子引起的，研究最深入的电荷转移（CT）带之一是与四硫富富烯（TTF）及其络合物络合的翠绿色带衍生品。最近在该期刊中基于理论气相计算对这种解释提出了质疑，该理论根据TTF与CBPQT（4+）的一个联吡啶（BIPY2 +）单元之一的分子间侧向相互作用重新解释了该CT波段。比CBPQT（4+）腔内的TTF封装要好。我们进行了DFT计算，包括溶剂化，最终表明，将TTF与CBPQT（4+）混合后出现的CT谱带是由1：1包合物形成的。为了支持该结论，我们对[2]轮烷进行了额外的实验，其中位于其短哑铃中间的TTF单元在空间上与CBPQT的两个BIPY2 +单元中的任一个相互作用（4 +）环以侧向方式驻留在单独的[2]轮烷上。该[2]轮烷具有与TTF及其衍生物与CBPQT（4+）的1：1包合物的相似的UV / Vis和（HNMR）-H-1光谱性质。 [2]轮烷以在其哑铃成分中与双取代的TTF单元缔合的顺式和反式异构体的等摩尔混合物形式存在。两种异构体均获得了固态结构，这证实了产生CT谱带的TTF单元位于CBPQT（4+）内部的结论。

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