Technological interest in the design of multifunctional microporous materia
ls has stimulated recent research into the development of mild solventother
mal techniques for the construction of lamellar and framework Main Group ch
alcogenidometalates. Reaction pathways from elemental or metal chalcogenide
sources can be influenced by a variety of often interdependent factors of
which counter cation size and charge, solvent polarity, pH and temperature
are of paramount importance. As reviewed in this article, the presence of p
redominant solution species such as cyclic tripyramidal M3S63- (M = As or S
b) or edge-bridged ditetrahedral Sn2E64- anions (E = S or Se) as molecular
building units and their participation in columnar substructures is charact
eristic for M2S3- and SnE2-based anionic networks. Hierarchical topological
relationships between individual members of structural families of the typ
e A(x)M(y)E(z) (A = alkali metal or alkylammonium cation) can be establishe
d that provide a detailed insight into probable multiple-step cation-direct
ed self-assembly mechanisms. These findings enable the development of ratio
nal guidelines for the employment of suitable counter cations in controllin
g the condensation of small solution species into chains, sheets or framewo
rks, whose cavities reflect the spatial requirements of the structure-direc
ting agent.