Synergistic regulation of nonbinary molecular switches by protonation and light
Synergistic regulation of nonbinary molecular switches by protonation and light
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DOI：
10.1073/pnas.2112973118
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发表时间：
2021-11-23
影响因子：
11.1
通讯作者：
Gong, Han-Yuan
中科院分区：
文献类型：
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作者：
Zhang, Xin;Yang, Yu-Dong;Gong, Han-Yuan
我们报告了一种分子开关整体，其状态可以通过质子化和光照射以协同方式调节。这允许在动力学和热力学意义上进行分级控制。这些基于拟轮烷的分子装置利用所谓的德克萨斯大小的分子盒（环[2]-（2,6-二（1Himidazol-1-yl）吡啶）[2]（1,4-二亚甲基苯）；1(4+)，以其四-PF6-盐的形式进行研究）作为轮组件。偶氮苯-4,4'-二甲酸(2H(+)中心点2)或4,4'-茋二甲酸(2H(+)中心点3)的阴离子用作穿线杆元件。 2 和 3 的各种形式（中性、单质子化和二质子化）与 1(4+) 的相互作用不同，这些经典光活性客体的光诱导顺式或反式形式也是如此。最终结果是多模式分子开关，可以通过质子化/去质子化和光照射以协同方式进行调节。客体质子化程度是主要控制因素，光充当次要调节刺激。目前的双输入策略为更传统的基于正交刺激的分子切换方法提供了补充，并允许创建非二元刺激响应功能材料。
We report a molecular switching ensemble whose states may be regulated in synergistic fashion by both protonation and photoirradiation. This allows hierarchical control in both a kinetic and thermodynamic sense. These pseudorotaxane-based molecular devices exploit the so-called Texas-sized molecular box (cyclo[2]-(2,6-di(1Himidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene); 1(4+), studied as its tetrakis-PF6- salt) as the wheel component. Anions of azobenzene-4,4'-dicarboxylic acid (2H(+)center dot 2) or 4,4'-stilbenedicarboxylic acid (2H(+)center dot 3) serve as the threading rod elements. The various forms of 2 and 3 (neutral, monoprotonated, and diprotonated) interact differently with 1(4+), as do the photoinduced cis or trans forms of these classic photoactive guests. The net result is a multimodal molecular switch that can be regulated in synergistic fashion through protonation/deprotonation and photoirradiation. The degree of guest protonation is the dominating control factor, with light acting as a secondary regulatory stimulus. The present dual input strategy provides a complement to more traditional orthogonal stimulus-based approaches to molecular switching and allows for the creation of nonbinary stimulus-responsive functional materials.