Twou nprecedented … …[ 5 +10] icosanuclear molecular 4-ravels containing four were designed rationally and synthesized successfully using as ingle-step strategy described by Li-Long Dang,G uo-Xin Jin et al. in their Research Article (e202301516). This new topology is achieved by utilizing parallel-displaced p•••p interactions carefully selected naphthoquinoyl Cp*M building blocks and X-shaped pyridyl ligands.

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.

Two unprecedented [5+10] icosanuclear molecular 4‐ravels containing four crossings were designed rationally and synthesized successfully using a single‐step strategy as described by Li‐Long Dang, Guo‐Xin Jin et al. in their Research Article (e202301516). This new topology is achieved by utilizing parallel‐displaced π⋅⋅⋅π interactions with carefully selected naphthoquinoyl Cp*M building blocks and X‐shaped pyridyl ligands.

No abstract