In Nature, complex molecular systems like proteins have evolved (natura nat
urans) which are perfectly suited to their functions. These are produced in
a sequence of steps under dissipative conditions-that is, far from equilib
rium. The challenge for the chemist is to nsynthesize correspondingly compl
ex multi-functional molecules also under non-equilibrium (non-dissipative)
conditions using multi-component, one-pot reactions, without having to sepa
rate and purify each single intermediate product. Relevant model reactions
have been discovered in solutions of simple oxoanions of the early transiti
on metals: novel types of molecular growth processes with feedback (includi
ng a type of induced cascade) are described leading to different ring-shape
d, electron-rich, mixed-valence, giant polyoxomolybdates with nanosized cav
ities. These can-due to the generation of defects-be covalently linked toge
ther to form chains as well as layered mesoporous compounds with properties
relevant for materials science. They can also start growing again. The lar
gest polyoxometalate cluster obtained on the basis of this growth process t
o-date has 248 Mo atoms. Remarkably, such giant ring species can also act a
s hosts for other clusters forming new types of supramolecular compounds. (
C) 1999 Elsevier Science S.A. All rights reserved.