A Modular Programmable Inorganic Cluster Discovery Robot for the Discovery and Synthesis of Polyoxometalates

[Image: see text] The exploration of complex multicomponent chemical reactions leading to new clusters, where discovery requires both molecular self-assembly and crystallization, is a major challenge. This is because the systematic approach required for an experimental search is limited when the number of parameters in a chemical space becomes too large, restricting both exploration and reproducibility. Herein, we present a synthetic strategy to systematically search a very large set of potential reactions, using an inexpensive, high-throughput platform that is modular in terms of both hardware and software and is capable of running multiple reactions with in-line analysis, for the automation of inorganic and materials chemistry. The platform has been used to explore several inorganic chemical spaces to discover new and reproduce known tungsten-based, mixed transition-metal polyoxometalate clusters, giving a digital code that allows the easy repeat synthesis of the clusters. Among the many species identified in this work, the most significant is the discovery of a novel, purely inorganic W(24)Fe(III)–superoxide cluster formed under ambient conditions. The modular wheel platform was employed to undertake two chemical space explorations, producing compounds 1–4: (C(2)H(8)N)(10)Na(2)[H(6)Fe(O(2))W(24)O(82)] (1, {W(24)Fe}), (C(2)H(8)N)(72)Na(16)[H(16)Co(8)W(200)O(660)(H(2)O)(40)] (2, {W(200)Co(8)}), (C(2)H(8)N)(72)Na(16)[H(16)Ni(8)W(200)O(660)(H(2)O)(40)] (3, {W(200)Ni(8)}), and (C(2)H(8)N)(14)[H(26)W(34)V(4)O(130)] (4, {W(34)V(4)}), along with many other known species, such as simple Keggin clusters and 1D {W(11)M(2+)} chains.