Highly Selective Synthesis of Iridium(III) Metalla[2]catenanes through Component Pre‐Orientation by π⋅⋅⋅π Stacking

Abstract

Aseries of molecular metalla[2]catenanes featuring Cp*Ir vertices have been prepared by the template-free, coordination-driven self-assembly of dinuclear iridium acceptors and 1,5-bis[2-(4-pyridyl)ethynyl]anthracene donors.T he metalla[2]catenanes were formed by using as trategically selected linker type that is capable of participating in sandwich-type p-p stackingi nteractions.I nt he solid state,t he [2]catenanes adopt two different configurations depending on the halogen atoms at the dinuclear metal complex bridge. Altering the solvent or the concentration, as well as the addition of guest molecules,e nabled controlled transformations between metalla[2]catenanes and tetranuclear metallarectangles.Scheme 1. Synthesis of the metallarectangles 1(OTf) 4 , 2a(OTf) 4 -4a(OTf) 4 ,a nd the metalla[2]catenanes 2(OTf) 8 -4(OTf) 8 .

Design of and Stability Studies on Trefoil Knots Featuring RhCp* Building Blocks

“…Metallasupramolecules have attracted increasing attention over the past few decades, mainly due to their diversea pplications [1] and fascinating aesthetics. [2] As interesti nt his fieldo f coordination chemistry has grown, complexesw ith aw ide range of topologies have been synthesized. The vast majority of the reported metallasupramoleculara rchitectures feature rigid building blocks with limitedf lexibility.I ng eneral, the utilization of rigid ligand precursors hampers the generation of isomersa nd increases the possibility of predicting and obtaining desired products.T he design and synthetic strategies employed in the field, whichh ave led to ab road variety of building blocksw ith different donor functions, have been discussed in an umber of contributions.…”

Non‐Covalent Interaction‐Directed Coordination‐Driven Self‐Assembly of Non‐Trivial Supramolecular Topologies

“…[31] The flexibility of L4 resulted in the formation of [1+1] complex with acceptor A6 along with the appropriate NCIs such as π−π and CH−π, to facilitate the catenation (Scheme 3). Recently, Jin and coworkers reported the synthesis of a series of [2]catenanes via the coordination‐driven self‐assembly of dinuclear Ir(III)‐based acceptors and 1,5‐bis[2‐(4‐pyridyl)ethynyl]anthracene donor ( L5 ) [11b] . The anthracene‐based donor L5 can participate in sandwich‐type π−π interactions.…”

Discrete Supramolecular Stacks Based on Multinuclear Tweezer‐Type Rhodium Complexes

“…Half-sandwich [Cp*M] (M = Ir,R h) [12,13] units have provent o be excellent buildingb locks for the construction of supramolecules. Although av arietyo ft opological structures based on these units have been assembled by following well-established design principles,t he preparation of molecular tweezers based on [Cp*M] fragments remains ag ap in this research field.…”