Automated reaction systems for the synthesis of complex inorganic clusters

• Main Author: Ruiz de la Oliva, Andreu
• Published: University of Glasgow 2014
• Subjects: 546; QD Chemistry
• Online Access: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.622043

Herein, the conventional method for the synthesis of polyoxometalate clusters (POMs) and the study of the formation mechanism is challenged by the development of a new reactor system. This is because two of the current limitations in POM synthesis are the difficulty of prediction, and control over the assembly of the final cluster. Further, the automation of the synthesis can provide reproducibility and robustness to the discovery approach. This thesis is devoted to the exploration of the synthetic parameters for the synthesis of POM compounds, and novel reactor platforms are presented, constructed and, finally, employed to perform POM synthesis. Herein, we present two configurable reactors which enable the control of the chemical composition, order of addition, and combine pumping sequences with in-situ analytics using a language based on unit operations. The networked reactor system (NRS) is employed to dynamically control, in space and time, the reaction conditions for the self-assembly of tungsten cluster libraries by connecting multiple “one-pot” reactors. The combination of the NRS with in-situ analytics allows us to synthesise and study the assembly of {W11}-based POMs by confining and connecting distinct building blocks to isolate larger clusters by a crystallization process. The controlled addition of inorganic templates using this particular synthetic approach allows us to study the assembly of POM in a programmable fashion, providing a new vision to the control in POM self-assembly. This led to the discovery of novel POM-based coordination compounds, such as the nano-scale anion cluster, [H16Co8W200O660(H2O)40]80-. The continuous processing system (CPS) shows the potential of continuous flow systems to perform multi batch POM synthesis for a wide range of nano-sized inorganic clusters in a highly controlled and reproducible fashion. The CPS allows the screening of large synthetic parameter spaces by systematically adjusting the reagent composition allowing us to rapidly target and discover inorganic clusters.