Discovery of gigantic molecular nanostructures using a flow reaction array as a search engine

The discovery of gigantic molecular nanostructures like coordination and polyoxometalate clusters is extremely time-consuming since a vast combinatorial space needs to be searched, and even a systematic and exhaustive exploration of the available synthetic parameters relies on a great deal of serendipity. Here we present a synthetic methodology that combines a flow reaction array and algorithmic control to give a chemical 'real-space' search engine leading to the discovery and isolation of a range of new molecular nanoclusters based on [Mo2O2S2](2+)-based building blocks with either fourfold (C-4) or fivefold (C-5) symmetry templates and linkers. This engine leads us to isolate six new nanoscale cluster compounds: 1, {Mo-10(C-5)}; 2, {Mo-14(C-4)(4)(C-5)(2)}; 3, {Mo-60(C-4)(10)}; 4, {Mo-48(C-4)(6)}; 5, {Mo-34(C-4)(4)}; 6, {Mo-18(C-4)(9)}; in only 200 automated experiments from a parameter space spanning similar to 5 million possible combinations.