The synthesis of water-sol., organometallic macrocycles is described. They were obtained by self-assembly in reactions of the half-sandwich complexes [{Ru(C6H5Me)Cl2}2], [{Ru(p-cymene)Cl2}2], [{Rh(Cp)Cl2}2], and [{Ir(Cp*)Cl2}2] with the ligand 5-dimethylaminomethyl-3-hydroxy-2-methyl-4-(1H)-pyridone in buffered aq. soln. at pH 8. The structure of the Ru-(p-cymene) complex was detd. by single-crystal X-ray crystallog. Upon mixing, these complexes undergo scrambling reactions to give dynamic combinatorial libraries. In combination with structurally related complexes based on amino-methylated 3-hydroxy-2-(1H)-pyridone ligands, an exchange of metal fragments but no mixing of ligands was obsd. This self-sorting behavior was used to construct dynamic combinatorial libraries of macrocycles, in which two four-component sub-libraries are connected by two common building blocks. This type of network topol. influences the adaptive behavior of the library as demonstrated in selection expts. with lithium ions as the target.