Although the selective synthesis of complicated supramolecular architectures has seen significant progress in recent years, the exploration of the properties of these complexes remains a fascinating challenge. Herein, a series of new supramolecular topologies, metalla2catenanes and Borromean ring assemblies, were constructed based on appropriate Cp*Rh building blocks and two rigid alkynyl pyridine ligands ( L1 , L2 ) via coordination-driven self-assembly. Interestingly, minor differences between the two rigid alkynyl pyridine ligands with/without organic substituents led to products with dramatically different topologies. Careful structural analysis showed that π-π stacking interactions play a crucial role in stabilizing these 2catenanes and Borromean ring assemblies, while also promoting nonradiative transitions and triggering photothermal conversion in both the solution and the solid states. These results were showcased through comparative studies of the NIR photothermal conversion efficiencies of the Borromean ring assemblies, 2catenanes and metallarectangles, which exhibited a wide range of photothermal conversion efficiencies (12.64-72.21%). The influence of the different Cp*Rh building blocks on the NIR photothermal conversion efficiencies of their assemblies was investigated. Good photothermal conversion properties of the assemblies were also found in the solid state. This study provides a new strategy to construct valuable half-sandwich-based NIR photothermal conversion materials while also providing promising candidates for the further development of materials science. The selective synthesis of three kinds of supermolecular topologies, molecular Borromean ring, 2catenane and metallarectangle based on two alkynyl ligands is presented. Remarkably, the NIR photothermal conversion efficiency was found to improve as the π-π stacking increases.