Arene Substitution Design for Controlled Conformational Changes of Dibenzocycloocta-1,5-dienes.
Arene Substitution Design for Controlled Conformational Changes of Dibenzocycloocta-1,5-dienes.
复制标题
芳烃取代设计控制二苯并环辛-1，5-二烯的构象变化。
DOI：
10.1021/jacs.0c06579
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发表时间：
2020-09-30
影响因子：
15
通讯作者：
Lu JQ
中科院分区：
文献类型：
--
作者：
Fu W;Alam TM;Li J;Bustamante J;Lien T;Adams RW;Teat SJ;Stokes BJ;Yang W;Liu Y;Lu JQ
我们报道了灵活的八元环烷烃可以通过稠合两个刚性苯环并被适当的官能团取代来稳定。二苯并环辛-1，5-二烯（DBCOD）是一种刚性-柔性-刚性有机分子，其构象从Boat构象转变为Chair构象所需的活化能为42 kJ/mol，远低于现有的亚分子形变单元的活化能。理论计算证实了实验数据表明，分子内氢键可以稳定船，而相反的酯取代基的电子排斥作用有利于椅子。由1，10-二酰胺取代形成的分子内氢键稳定了Boat，使Boat和Chair可以在-60 °C到60 °C之间轻松互换的温度飙升。同时，这种分子内吸引力将能垒从未取代的DBCOD的42 kJ/mol提高到二酰胺取代的DBCOD的68 kJ/mol。值得注意的是，该值福尔斯落在高效酶催化生物反应的活化能范围内。形状变化曾经被认为只有在高能量下才有可能，我们的工作揭示了一种潜在的途径，以特定的亚分子结构为例，首次实现了低能量驱动的形状变化。与内在循环稳定性和高能量输出系统一起，这些系统在高能量刺激下会受到损害，特别是可以从这种新型的低能量驱动的形状改变机制中受益。这项工作为构建低能量驱动的刺激响应应用系统奠定了基础，迄今为止这是一个有待克服的挑战。
We report that the agile eight-membered cycloalkane can be stabilized by fusing two rigid benzene rings, substituted with proper functional groups. The conformational change of dibenzocycloocta-1,5-diene (DBCOD), a rigid-flexible-rigid organic moiety, from Boat to Chair conformation requires an activation energy of 42 kJ/mol that is substantially lower than that of existing submolecular shape-changing unit. Experimental data corroborated by theory calculations demonstrate that intramolecular hydrogen bonding can stabilize Boat whereas electron repulsive interaction from opposing ester substituents favors Chair. Intramolecular hydrogen bonding, formed by 1,10-diamide substitution stabilizes Boat, spiking the temperature at which Boat and Chair can readily interchange from −60 °C to 60 °C. Concomitantly this intramolecular attraction raises the energy barrier from 42 kJ/mol of unsubstituted DBCOD to 68 kJ/mol of diamide-substituted DBCOD. Remarkably, this value falls within the range of the activation energy of highly efficient enzyme catalyzed biological reactions. With shape changes once considered only possible with high-energy, our work reveals a potential pathway exemplified by a specific submolecular structure to achieve low-energy driven shape changes for the first time. Together with intrinsic cycle stability and high energy output systems that would have incurred damage under high-energy stimuli, could particularly benefit from this new kind of low-energy driven shape-changing mechanism. This work has laid the basis to construct systems for low-energy driven stimuli-responsive applications, hitherto a challenge to overcome.
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DOI：
10.1039/jr9450000027
发表时间：
1945-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY
影响因子：
--
作者：
BAKER, W;BANKS, R;MANN, FG
通讯作者：
MANN, FG
影响因子：
29.4
作者：
de Villeneuve, Catherine Henry;Michalik, Fabian;Allongue, P.
通讯作者：
Allongue, P.
DOI：
10.1002/anie.201611325
发表时间：
2017-03-13
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Aßhoff SJ;Lancia F;Iamsaard S;Matt B;Kudernac T;Fletcher SP;Katsonis N
通讯作者：
Katsonis N
影响因子：
15
作者：
Hammerich, Melanie;Schuett, Christian;Herges, Rainer
通讯作者：
Herges, Rainer
影响因子：
2.9
作者：
Crecca, Christina R.;Roitberg, Adrian E.
通讯作者：
Roitberg, Adrian E.