Herein, one interdigitated molecular and two metallarectangles were realized successfully using two rigid bidentate ligands (L1, L2) and two building blocks (E1, E2) via coordination-driven self-assembly strategy. Interestingly, a novel interdigitated structure has been successfully formed through triple π-π stacking interactions, different from the previously reported interlocked 2catenanes. Based on the π-π stacking interaction, nonradiative transitions were promoted and obvious photothermal transitions effect was triggered in solution and solid states. In addition, it is found that the interdigitated structure has a decent photothermal conversion efficiency of about 12% in solution state. This study provides open up new ideas for our future development of near-infrared photothermal conversion materials. A series of discrete metallarectangles and an interdigitated molecule were synthesized by coordination-driven self-assembly. These topologies were unambiguously confirmed by NMR spectroscopy, ESI-MS, IR spectroscopy as well as X-ray crystallography. In addition, triple π-π stacking interactions were found in the interdigitated structure, which results in the capability of photothermal conversion. Display omitted •One interdigitated molecular and two metallarectangles were realized successfully using two rigid bidentate ligands and two building blocks via coordination-driven self-assembly strategy.•The interdigitated structure was constructed through triple π-π stacking interactions, different from the previously reported interlocked 2catenanes, which result in nonradiative transitions and trigger photothermal conversion in both the solution and the solid states.•The photothermal conversion study exhibits a good photothermal conversion efficiency (12%) for the interdigitated structure at 660 ​nm in the solution state. This study provides open up new ideas for our future development of near-infrared photothermal conversion materials.