Variations in the fuel structure control the rate of the back and forth motions of a chemically fuelled molecular switch.
Variations in the fuel structure control the rate of the back and forth motions of a chemically fuelled molecular switch.
复制标题
燃料结构的变化控制化学燃料分子开关的来回运动速率。
DOI：
10.1039/c7sc04123c
复制
发表时间：
2018-01-07
期刊：
影响因子：
8.4
通讯作者：
Di Stefano S
中科院分区：
文献类型：
--
作者：
Biagini C;Albano S;Caruso R;Mandolini L;Berrocal JA;Di Stefano S
燃料结构中的适度变化引起化学燃料的基于悬链线的开关所经历的来回运动的速率的大的变化。本工作涉及使用2-氰基-2-芳基丙酸作为化学燃料的酸碱操作的分子开关，由一个Sauvage型链组成的两个相同的大环，并纳入一个菲咯啉单元。当用作丙酸衍生物的脱羧的碱基促进剂时，开关经历从中性链状物到质子化链状物的大幅度运动，并再次回到中性状态。反质子转移速率决定了整个过程的速率，对位取代基对反质子转移速率的影响顺序为Cl > H > CH 3> OCH 3（ρ = +5.2）。因此，对于OCH 3衍生物，完成一个完整循环所需的时间几乎为两天，而对于Cl衍生物，则降至几分钟。这些结果首次表明，分子开关的操作速率可以通过燃料结构的变化来调节。
Moderate variations in the fuel structure cause large changes in the rate of the back and forth motions experienced by a chemically fuelled catenane-based switch. This work deals with the use of 2-cyano-2-arylpropanoic acids as chemical fuels for an acid–base operated molecular switch that consists of a Sauvage-type catenand composed of two identical macrocycles incorporating a phenanthroline unit. When used as a base promoter of the decarboxylation of propanoic acid derivatives, the switch undergoes large amplitude motion from the neutral catenand to a protonated catenate and back again to the neutral state. The rate of back proton transfer, which determines the rate of the overall process, was markedly affected by para-substituents in the order Cl > H > CH3 > OCH3 (ρ = +5.2). Thus, the time required to complete a full cycle was almost two days for the OCH3 derivative and dropped to a few minutes for the Cl derivative. These results show for the first time that the rate of operation of a molecular switch can be regulated by variations in the fuel structure.
登录
查看更多内容
DOI：
10.1073/pnas.0509011103
发表时间：
2006-01-31
影响因子：
11.1
作者：
Balzani, V;Clemente-León, M;Stoddart, JF
通讯作者：
Stoddart, JF
影响因子：
15
作者：
Armaroli, N;Balzani, V;Ventura, B
通讯作者：
Ventura, B
影响因子：
15
作者：
CRAMER, F;KAMPE, W
通讯作者：
KAMPE, W
影响因子：
16.6
作者：
Berrocal, Jose Augusto;Biagini, Chiara;Di Stefano, Stefano
通讯作者：
Di Stefano, Stefano
影响因子：
4.3
作者：
Baroncini, Massimo;Silvi, Serena;Credi, Alberto
通讯作者：
Credi, Alberto