Ruiz de la Oliva Andreu, Sans Victor, Miras Haralampos N, Long De-Liang, Cronin Leroy
WestCHEM, School of Chemistry, The University of Glasgow , Glasgow G12 8QQ, Scotland, U.K.
Inorg Chem. 2017 May 1;56(9):5089-5095. doi: 10.1021/acs.inorgchem.7b00206. Epub 2017 Apr 17.
Chemical transformations are normally conducted in batch or flow mode, thereby allowing the chemistry to be temporally or spatially controlled, but these approaches are not normally combined dynamically. However, the investigation of the underlying chemistry masked by the self-assembly processes that often occur in one-pot reactions and exploitation of the potential of complex chemical systems requires control in both time and space. Additionally, maintaining the intermediate constituents of a self-assembled system "off equilibrium" and utilizing them dynamically at specific time intervals provide access to building blocks that cannot coexist under one-pot conditions and ultimately to the formation of new clusters. Herein, we implement the concept of a programmable networked reaction system, allowing us to connect discrete "one-pot" reactions that produce the building block{WO} ≡ {W} under different conditions and control, in real time, the assembly of a series of polyoxometalate clusters {WO} ≡ {W}, {WO} ≡ {W} 1a, {WO} ≡ {W} 2a, and {WO} ≡ {W} 3a, using pH and ultraviolet-visible monitoring. The programmable networked reaction system reveals that is possible to assemble a range of different clusters using {W}-based building blocks, demonstrating the relationship between the clusters within the family of iso-polyoxotungstates, with the final structural motif being entirely dependent on the building block libraries generated in each separate reaction space within the network. In total, this approach led to the isolation of five distinct inorganic clusters using a "fixed" set of reagents and using a fully automated sequence code, rather than five entirely different reaction protocols. As such, this approach allows us to discover, record, and implement complex one-pot reaction syntheses in a more general way, increasing the yield and reproducibility and potentially giving access to nonspecialists.
化学转化通常以间歇或流动模式进行，从而使化学反应能够在时间或空间上得到控制，但这些方法通常不会进行动态结合。然而，对于在一锅法反应中经常发生的自组装过程所掩盖的潜在化学反应的研究以及对复杂化学体系潜力的开发，需要在时间和空间上都进行控制。此外，使自组装体系的中间成分保持“非平衡”状态，并在特定时间间隔动态利用它们，能够获得在一锅法条件下无法共存的结构单元，并最终形成新的簇。在此，我们实现了可编程网络反应系统的概念，该系统使我们能够连接在不同条件下产生结构单元{WO}≡{W}的离散“一锅法”反应，并利用pH值和紫外-可见监测实时控制一系列多金属氧酸盐簇{WO}≡{W}、{WO}≡{W} 1a、{WO}≡{W} 2a和{WO}≡{W} 3a的组装。可编程网络反应系统表明，使用基于{W}的结构单元可以组装一系列不同的簇，展示了同多钨酸盐家族中各簇之间的关系，最终的结构基序完全取决于网络中每个单独反应空间内生成的结构单元库。总体而言，这种方法使用一组“固定”的试剂并通过完全自动化的序列编码，成功分离出了五个不同的无机簇，而不是五种完全不同的反应方案。因此，这种方法使我们能够以更通用的方式发现、记录和实施复杂的一锅法反应合成，提高产率和重现性，并有可能让非专业人员也能进行操作。
