Rational Design and Synthesis of Interlocked [2]Catenanes Featuring Half‐Sandwich Cp*Rh/Ir Units and Pyrene‐Based Ligands†

Main observation and conclusion The construction of interlocked topologies by metal‐cation‐template methods has been extensively explored. However, construction of these species using template‐free chemical self‐assembly methods is hard to rationally achieve due to the inherent unpredictability of self‐assembly processes. In this work, a strategy to construct interlocked [2]catenanes by coordination‐driven template‐free self‐assembly is demonstrated, whereby combining rigid bidentate ligands with large conjugated‐π area units and building blocks with appropriate lengths facilitated construction of interlocked [2]catenane compounds. Two rigid bidentate ligands, L1 and L2, were chosen to self‐assemble with three dinuclear building blocks B1, B2 and B3. Ultimately, the successful construction of three [2]catenanes demonstrated the validity of the strategy. Although [2]catenanes are the simplest of all interlocked topologies, this motif is the basis for constructing more intricate topologies. This successful strategy may therefore lead to construction of other, more intricate topologies in the future.