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 Fe4 (AD2 )6 22-component cage 1, dinuclear Fe2 (BD2 )3 11-component helicate 2, and 5-component mononuclear Fe(CD3 ) complex 3 were prepared simultaneously in a one-pot reaction from 38 components. Through subcomponent substitution reaction by adding subcomponent B, the Fe4 (AD2 )6 cage converts quantitatively to the Fe2 (BD2 )3 helicate, which, in turn, upon addition of subcomponent C, transforms to Fe(CD3 ) , following the hierarchical preference based on the thermodynamic stability of the complexes.