The Covalent and Coordination Co-Driven Assembly of Supramolecular Octahedral Cages with Controllable Degree of Distortion

Discovering
and constructing novel and fancy structures is the
goal of many supramolecular chemists. In this work, we propose an
assembly strategy based on the synergistic effect of coordination
and covalent interactions to construct a set of octahedral supramolecular
cages and adjust their degree of distortion. Our strategy innovatively
utilizes the addition of sulfur atoms of a metal sulfide synthon,
[Et4N]­[Tp*WS3] (A), to an alkynyl
group of a pyridine-containing linker, resulting in a novel vertex
with low symmetry, and of Cu­(I) ions. By adjusting the length of the
linker and the position of the reactive alkynyl group, the control
of the deformation degree of the octahedral cages can be realized.
These supramolecular cages exhibit enhanced third-order nonlinear
optical (NLO) responses. The results offer a powerful strategy to
construct novel distorted cage structures as well as control the degree
of distortion of supramolecular geometries.