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 [Mo(2)O(2)S(2)](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 ~5 million possible combinations.