Trace mild acid-catalysed Z → E isomerization of norbornene-fused stilbene derivatives: intelligent chiral molecular photoswitches with controllable self-recovery.
Trace mild acid-catalysed Z → E isomerization of norbornene-fused stilbene derivatives: intelligent chiral molecular photoswitches with controllable self-recovery.
复制标题
痕量中性酸催化的Z→E异构化的异构化的肾融合衍生物：具有可控制的自我恢复的智能手性分子照片开关。
DOI：
10.1039/d0sc05213b
复制
发表时间：
2020-12-28
期刊：
影响因子：
8.4
通讯作者：
Yang C
中科院分区：
文献类型：
--
作者：
Hao T;Yang Y;Liang W;Fan C;Wang X;Wu W;Chen X;Fu H;Chen H;Yang C
二苯乙烯衍生物长期以来一直被认为会发生“酸催化”的Z → E异构化，其中高浓度的强无机酸在实践中是必要的。这种苛刻的反应条件经常引起不希望的副反应并限制它们的潜在应用。在此，我们提出了一个微量的温和的酸催化的Z → E异构化发现与芪衍生物稠合的一个异戊烯部分。副反应，如CC双键的迁移和亲电加成反应，完全抑制，因为环的应变所造成的稠合环己烯组分。E异构体在选定波长下的直接光解导致这些二苯乙烯衍生物的E → Z光异构化，从而构成了一类独特的可由光和酸正交控制的分子开关。催化量的酸可以容易地去除，并且Z → E异构化可以通过打开/关闭光酸的照射来控制，这允许以非侵入性方式重复异构化。此外，在催化量的酸存在下，光异构化产生的Z异构体可以自发地自恢复为E异构体。Z → E异构化的动力学可通过控制催化因子进行调节，从而实现了前所未有的具有可调节自恢复的分子光开关。微量弱酸催化定量Z → E异构化，提供酸和光正交可控的分子开关。
Stilbene derivatives have long been known to undergo “acid-catalyzed” Z → E isomerization, where a strong mineral acid at high concentration is practically necessary. Such severe reaction conditions often cause undesired by-reactions and limit their potential application. Herein, we present a trace mild acid-catalyzed Z → E isomerization found with stilbene derivatives fused with a norbornene moiety. By-reactions, such as the migration of the CC double bond and electrophilic addition reactions, were completely inhibited because of the ring strain caused by the fused norbornene component. Direct photolysis of the E isomers at selected wavelengths led to the E → Z photoisomerization of these stilbene derivatives and thus constituted a unique class of molecular switches orthogonally controllable by light and acid. The catalytic amount of acid could be readily removed, and the Z → E isomerization could be controlled by turning on/off the irradiation of a photoacid, which allowed repeated isomerization in a non-invasive manner. Moreover, the Z isomer produced by photoisomerization could spontaneously self-recover to the E isomer in the presence of a catalytic amount of acid. The kinetics of Z → E isomerization were adjustable by manipulating catalytic factors and, therefore, unprecedented molecular photoswitches with adjustable self-recovery were realized. Quantitative Z → E isomerization was catalyzed by trace mild acids to offer molecular switches orthogonally controllable by acid and light.
登录
查看更多内容
燃料结构的变化控制化学燃料分子开关的来回运动速率。
影响因子：
8.4
作者：
Biagini C;Albano S;Caruso R;Mandolini L;Berrocal JA;Di Stefano S
通讯作者：
Di Stefano S
影响因子：
12.9
作者：
Chew, Alex K.;Walker, Theodore W.;Van Lehn, Reid C.
通讯作者：
Van Lehn, Reid C.
影响因子：
15
作者：
Goulet-Hanssens, Alexis;Utecht, Manuel;Hecht, Stefan
通讯作者：
Hecht, Stefan
影响因子：
15
作者：
Fleming, Cassandra L.;Li, Shiming;Andreasson, Joakim
通讯作者：
Andreasson, Joakim
影响因子：
15
作者：
Cvrtila I;Fanlo-Virgós H;Schaeffer G;Monreal Santiago G;Otto S
通讯作者：
Otto S