Solvent‐Free Ball‐Milling Subcomponent Synthesis of Metallosupramolecular Complexes

Subcomponent self‐assembly from components A , B , C , D , and Fe 2+ under solvent‐free conditions by self‐sorting leads to the construction of three structurally different metallosupramolecular iron(II) complexes. Under carefully selected ball‐milling conditions, tetranuclear [Fe 4 ( AD 2 ) 6 ] 4− 22‐component cage 1 , dinuclear [Fe 2 ( BD 2 ) 3 ] 2− 11‐component helicate 2 , and 5‐component mononuclear [Fe( CD 3 )] 2+ complex 3 were prepared simultaneously in a one‐pot reaction from 38 components. Through subcomponent substitution reaction by adding subcomponent B , the [Fe 4 ( AD 2 ) 6 ] 4− cage converts quantitatively to the [Fe 2 ( BD 2 ) 3 ] 2− helicate, which, in turn, upon addition of subcomponent C , transforms to [Fe( CD 3 )] 2+ , following the hierarchical preference based on the thermodynamic stability of the complexes.