Spontaneous formation of autocatalytic sets with self-replicating inorganic metal oxide clusters
Haralampos N. Miras, Cole Mathis, Weimin Xuan, De‐Liang Long, Robert Pow, Leroy Cronin
Abstract
Here we show how a simple inorganic salt can spontaneously form autocatalytic sets of replicating inorganic molecules that work via molecular recognition based on the {PMo 12 } ≡ [PMo 12 O 40 ] 3– Keggin ion, and {Mo 36 } ≡ [H 3 Mo 57 M 6 (NO) 6 O 183 (H 2 O) 18 ] 22– cluster. These small clusters are able to catalyze their own formation via an autocatalytic network, which subsequently template the assembly of gigantic molybdenum-blue wheel {Mo 154 } ≡ [Mo 154 O 462 H 14 (H 2 O) 70 ] 14– , {Mo 132 } ≡ [Mo VI 72 Mo V 60 O 372 (CH 3 COO) 30 (H 2 O) 72 ] 42– ball-shaped species containing 154 and 132 molybdenum atoms, and a {PMo 12 }⊂{Mo 124 Ce 4 } ≡ [H 16 Mo VI 100 Mo V 24 Ce 4 O 376 (H 2 O) 56 (PMo VI 10 Mo V 2 O 40 )(C 6 H 12 N 2 O 4 S 2 ) 4 ] 5– nanostructure. Kinetic investigations revealed key traits of autocatalytic systems including molecular recognition and kinetic saturation. A stochastic model confirms the presence of an autocatalytic network involving molecular recognition and assembly processes, where the larger clusters are the only products stabilized by the cycle, isolated due to a critical transition in the network.