A variety of organometallic supramolecular architectures
have been
constructed over the past decades and their properties were also explored
via different strategies. However, the synthesis of metalla-Russian
doll is still a fascinating challenge. Herein, a series of new coordination
supramolecular complexes, including a metalla-Russian doll, metalla[2]catenanes,
and metallarectangles, were synthesized by using meticulously selected
Cp*Rh (Cp* = η5-C5Me5) building
units (E1, E2, and E3) and three rigid anthracylpyridine ligands (L1,
L2, and L3) via a self-assembly strategy. While the combination of
the short ligand L1 and E1 or E2 generated two metallarectangles,
the longer ligand L2 containing an alkynyl group resulted in two new
[2]catenanes, most likely due to which the strong electron-donating
effect of alkynyl groups causes self-accumulation. Interestingly,
an unusual Russian doll assembly was obtained through the reaction
of L3 and E3 based on sextuple π···π stacking
interactions. Furthermore, the dynamic structural conversion between
[2]catenanes and the corresponding metallarectangles could be observed
through concentration-, solvent-, and guest-induced effects. The [2]catenane
complexes 4b displayed efficient photothermal conversion efficiency
in solution (20.2%), in comparison with other organometallic macrocycles.
We believe that π···π stacking interactions
generate active nonradiative pathways and promote radiative photodeactivation
pathways. This study proves the versatility of half-sandwich building
units, not only to build complicated supramolecular topologies but
also in effective functional materials for various appealing applications.