In summary, five novel copper(I) halides-based coordination
polymers have been obtained. The synergism of the potentially polydentate
bridging HMTZ ligand and the effectiveness of the halide
ions in adopting bridging modes provide complex connectivity patterns
and remarkable structural diversity. Complex 1 displays a 1D
chain with [Cu3Cl3] motifs as repeating unit. Complexes 2 and 1
are polymorphism, which shows 2D inorganic–organic network
with [Cu6Cl6]. And 3 and 2 are isomorphism, which the chlorine
atoms are replaced by the bromine atoms. 4 exhibits a propeller-like
[Cu4] cluster. 5 exhibits a flower basket-like [Cu8] cluster basing on
an iodine template effect and the crystal structures reveal a correlation
between the size and nature of the anionic guest with the
dimensions of the Cu8 metallacycle host, making remarkable the
elasticity of the copper crown self-assembly. Complexes 1–5 exhibit
weak fluorescence emissions in the solid state at room temperature.
Accordingly, this work represents a suitable method to separate and
stabilize the CumXn motifs through HMTZ, which will encourage us
to make a further research on related functional crystalline solids
via such a reliable synthetic procedure.