A catenane assembled through a single charge-assisted halogen bond.
A catenane assembled through a single charge-assisted halogen bond.
复制标题
DOI：
10.1002/anie.201300464
复制
发表时间：
2013-04-15
影响因子：
16.6
通讯作者：
Beer, Paul D.
中科院分区：
文献类型：
--
作者：
Gilday, Lydia C.;Lang, Thomas;Caballero, Antonio;Costa, Paulo J.;Felix, Vitor;Beer, Paul D.
互锁分子由于其非平凡的拓扑结构和其作为分子机器[1]和化学传感器应用的潜在纳米技术用途的前景而吸引了化学家的想象力。[2]这种复杂结构的合成是一个挑战，因此这需要实施富有想象力的阳离子，[3]阴离子，[4]和中性[5]模板方法，其使用互补的刘易斯酸碱，静电和氢键相互作用的组合进行组件组装。卤素键（XB）是指缺电子卤素原子与刘易斯碱之间具有高度方向性的非共价相互作用。[6]XB在固态晶体工程中的应用范围已经被深入探索了许多年，[7]然而，尽管与无处不在的氢键有互补的相似性，但直到最近才对溶液相XB相互作用在分子识别过程，自组装和催化中的应用进行了研究，导致这一领域迅速发展。[8]事实上，结合阴离子模板，我们已经使用XB组装互穿和互锁的分子框架。[8b-d]通过将合适的中性刘易斯碱XB受体，如吡啶[7 b，9]引入大环骨架中，我们在此证明了单一电荷辅助的XB相互作用可用于伪轮烷组装，并且重要的是，可用于合成新的互锁索烃。非环状带正电荷的XB-供体组分穿过互补的接受XB的含吡啶的大环，从而形成通过电荷辅助的XB相互作用稳定的正交互穿组装体。除了并入的吡啶XB-受体基序之外，大环组分1含有富电子氢醌基团以促进补充的仲芳族供体-受体与缺电子带正电荷的杂环XB-供体穿线衍生物的相互作用。选择一系列溴-和碘官能化的三唑钥和吡啶钥化合物作为潜在的穿线组分，其含有末端乙烯基官能团，其在与大环1成功的假轮烷组装后，可用于通过闭环复分解（RCM）环化的索烃合成（方案1）。大环1和卤代官能化的三唑鎓和吡啶鎓衍生物通过如下制备：
Interlocked molecules have captured chemists imagination owing to their nontrivial topology and the promise of their potential nanotechnological uses as molecular machines [1] and in chemical sensor applications.[2] The synthesis of such sophisticated architectures is a challenge, and as a consequence this has necessitated the implementation of imaginative cation,[3] anion,[4] and neutral [5] templation methodologies, which use a combination of complementary Lewis acid–base, electrostatic, and hydrogen-bonding interactions for component assembly. Halogen bonding (XB) is the attractive highly directional, noncovalent interaction between an electron-deficient halogen atom and a Lewis base.[6] The scope of XB in solid-state crystal engineering has been intensively explored for a number of years,[7] however, in spite of the complementary analogy to ubiquitous hydrogen bonding, it is only in recent times that investigations into the application of solution-phase XB interactions to molecular recognition processes, self-assembly, and catalysis have resulted in this field developing rapidly.[8] Indeed, in conjunction with anion templation, we have used XB to assemble interpenetrated and interlocked molecular frameworks.[8b–d] By incorporating a suitable neutral Lewis base XB acceptor, such as pyridine,[7b, 9] into a macrocyclic framework, we demonstrate herein that a single charge-assisted XB interaction can be utilized for pseudorotaxane assembly and, importantly, in the synthesis of a novel interlocked catenane.The synthetic strategy employed to construct the target catenane is outlined in Figure 1. An acyclic positively charged XB-donor component threads through a complementary XB-accepting pyridine-containing macrocycle, thereby forming an orthogonal interpenetrative assembly that is stabilized by a charge-assisted XB interaction. In addition to the incorporated pyridine XB-acceptor motif, the macrocycle component 1 contains electron-rich hydroquinone groups to facilitate supplementary secondary aromatic donor–acceptor interactions with electron-deficient positively charged heterocyclic XB-donor threading derivatives. A range of bromo-and iodofunctionalized triazolium and pyridinium compounds were chosen as potential threading components, containing terminal vinyl functional groups, which after successful pseudorotaxane assembly with macrocycle 1, could be used for catenane synthesis through ring-closing metathesis (RCM) cyclization (Scheme 1). Macrocycle 1 and halo-functionalized triazolium and pyridinium derivatives were prepared by using
登录
查看更多内容
影响因子：
3.3
作者：
Bruce, Duncan W.;Metrangolo, Pierangelo;Whitwood, Adrian C.
通讯作者：
Whitwood, Adrian C.
影响因子：
15
作者：
Kilah, Nathan L.;Wise, Matthew D.;Beer, Paul D.
通讯作者：
Beer, Paul D.
影响因子：
4.9
作者：
Curiel, D;Beer, PD
通讯作者：
Beer, PD
影响因子：
4.3
作者：
Cincic, Dominik;Friscic, Tomislav;Jones, William
通讯作者：
Jones, William
影响因子：
3.3
作者：
Rendine, Stefano;Pieraccini, Stefano;Sironi, Maurizio
通讯作者：
Sironi, Maurizio