Selective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes.
Selective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes.
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苝二酰亚胺-柱[5]芳烃轮烷的选择性光诱导电荷分离。
DOI：
10.1038/s41467-022-28022-3
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发表时间：
2022-01-20
影响因子：
16.6
通讯作者：
Champness NR
中科院分区：
文献类型：
--
作者：
Pearce N;Reynolds KEA;Kayal S;Sun XZ;Davies ES;Malagreca F;Schürmann CJ;Ito S;Yamano A;Argent SP;George MW;Champness NR
控制分子内光致电荷转移的能力是一个重大挑战，需要精确控制给体和受体基团的相对位置和取向。在这里，我们证明了同位和杂位轮烷中的这种光致电荷转移过程可以通过机械互锁分子的组件的组织来控制，从而引入了电子给予的替代路径。具体地说，描述了两种轮烷的研究：一种是同[3]轮烷，由缠绕两个柱状[5]芳烃大环的螺二酰亚胺二咪唑杆构建；另一种是杂[4]轮烷，其中附加的二(1，5-萘基)-38-冠-10(BN38C10)大环环绕着中心的螺二亚胺。这两种轮烷的特征是结合了多种技术，包括电子衍射、结晶学和杂环轮烷[4]。循环伏安法、光谱电化学和EPR光谱被用来确定这两种轮烷的氧化还原态的行为，这些数据被用来为使用时间分辨红外(TRIR)和瞬时吸收(TA)光谱的光物理研究提供信息。后者的研究表明，在高[3]轮烷的情况下，只涉及两个大环组分中的一个，观察到柱状[5]芳烃和二苯二亚胺之间的电荷转移，从而形成了对称破坏电荷分离态。在杂环[4]轮烷的情况下，只观察到BN38C10大环和二苯二亚胺的电荷分离，柱[5]芳烃组分没有受到干扰。复杂分子机械的发展需要对通过纳米级支架控制能量通路的因素进行详细的评估。在这里，作者证明了杂轮烷可以被用来产生不同氧化还原和光活性成分的组装，从而能够选择性地调节能量转移路径。
The ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homo[3]rotaxane, built from a perylenediimide diimidazolium rod that threads two pillar[5]arene macrocycles, and a hetero[4]rotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combination of techniques including electron diffraction crystallography in the case of the hetero[4]rotaxane. Cyclic voltammetry, spectroelectrochemistry, and EPR spectroscopy are employed to establish the behaviour of the redox states of both rotaxanes and these data are used to inform photophysical studies using time-resolved infra-red (TRIR) and transient absorption (TA) spectroscopies. The latter studies illustrate the formation of a symmetry-breaking charge-separated state in the case of the homo[3]rotaxane in which charge transfer between the pillar[5]arene and perylenediimide is observed involving only one of the two macrocyclic components. In the case of the hetero[4]rotaxane charge separation is observed involving only the BN38C10 macrocycle and the perylenediimide leaving the pillar[5]arene components unperturbed. The development of complex molecular machinery requires a detailed appreciation of the factors that control energy pathways through the nanoscale scaffold. Here, the authors demonstrate that hetero-rotaxanes can be employed to create assemblies of different redox and photo-active components that enable selective tuning of energy transfer pathways.
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影响因子：
62.1
作者：
Gruene T;Mugnaioli E
通讯作者：
Mugnaioli E
影响因子：
3.1
作者：
Ito, Sho;White, Fraser J.;Meyer, Mathias
通讯作者：
Meyer, Mathias
使用电子衍射的微晶分子化合物的快速结构测定。
DOI：
10.1002/anie.201811318
发表时间：
2018-12-10
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Gruene T;Wennmacher JTC;Zaubitzer C;Holstein JJ;Heidler J;Fecteau-Lefebvre A;De Carlo S;Müller E;Goldie KN;Regeni I;Li T;Santiso-Quinones G;Steinfeld G;Handschin S;van Genderen E;van Bokhoven JA;Clever GH;Pantelic R
通讯作者：
Pantelic R
影响因子：
4.3
作者：
Delavaux-Nicot, Beatrice;Ben Aziza, Haifa;Nierengarten, Jean-Francois
通讯作者：
Nierengarten, Jean-Francois
影响因子：
15
作者：
Kuss-Petermann, Martin;Wenger, Oliver S.
通讯作者：
Wenger, Oliver S.