R. Kramer et al., SELF-RECOGNITION IN HELICATE SELF-ASSEMBLY - SPONTANEOUS FORMATION OFHELICAL METAL-COMPLEXES FROM MIXTURES OF LIGANDS AND METAL-IONS, Proceedings of the National Academy of Sciences of the United Statesof America, 90(12), 1993, pp. 5394-5398
On treatment with copper(I) ions, mixtures of the [oligo(2,2')-bipyrid
ine] strands 2-5 yield spontaneously the double helicates 2H(2)-2H(5)
without significant crossover. Similarly, when a mixture of the two tr
is-bypyridine ligands 1 and 3a (containing different substitutions) is
allowed to react with copper(I) and nickel(II) ions, only the double
helicate 2H(3a) and the triple helicate 3H(1) are formed. Thus, these
systems undergo self-assembly of helicates with self-recognition. The
process represents a self/nonself-discrimination involving the prefere
ntial binding of like metal ions by like ligand strands in a mixture t
o selectively assemble into the corresponding helicates. In a broader
perspective, these results point to a change in paradigm from pure com
pounds to instructed mixtures-that is from seeking chemical purity to
designing programmed systems composed of mixtures of instructed compon
ents capable of spontaneously forming well-defined superstructures thr
ough self-processes.