Quantitative Formation of [2]Catenanes Using Copper(I) and Palladium(II) as Templating and Assembling Centers:  The Entwining Route and the Threading Approach

Abstract

Transition metal-mediated templating and self-assembly have shown powerful potentials for the synthesis of interlocked molecules. These two strategies were combined in designing and preparing a new type of coordination catenanes incorporating Cu(I) and Pd(II) metal centers. The ligand designed here contains a phenanthroline core and pyridine sidearms (compound 1). Using this phenanthroline-pyridine conjugated ligand, two approaches were examined, which were shown to be surprisingly efficient for the catenane synthesis: the entwining route (entwining of two ligands around Cu(I) followed by Pd(II) clipping) and the threading approach (Cu(I)-templated threading of a cyclic ligand on an acyclic ligand followed by the Pd(II) clipping of the second ring). In the former method, stepwise treatment of 1 with Cu(CH(3)CN)(4)PF(6) (templating center) and enPd(NO(3))(2) (assembling center) gives rise to the quantitative formation of CuPd(2) catenane 18. In the latter method, Cu(I) templates the threading of phenanthroline-containing macrocycle 2 on ligand 1, which is followed by Pd(II) clipping to give hetero catenane 20. In both approaches, the formation of catenanes is convincing thanks to the strong templating effect of Cu(I), while the ring closure steps are efficiently furnished by Pd(II)-directed self-assembly.

Structure Switching and Modulation of the Magnetic Properties in Diarylethene‐Bridged Metallosupramolecular Compounds by Controlled Coordination‐Driven Self‐Assembly

“…[1] In particular,the coordination-driven self-assembly is apowerful route for synthesising "programmed" molecules with diverse architectures and physicochemical properties,including magnetic and luminescence properties. [2] Over the previous few decades,t he Lehn [3] and Sauvage [4] groups have conducted pioneering research related to the feasibility and utility of coordination-driven self-assembly for the formation of diverse structures,m ainly by controlling the kinetic and thermodynamic processes.F urthermore,t he research groups of Stang, [5] Fujita, [6] Mirkin, [7] Nitschke, [8] Shionoya, [9] and others [10] have exploited novel paradigms for the self-assem-bly of discrete metallacycles and metallacages with welldefined shapes and sizes.…”

Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung

“…Ebenso wie Dreifachknoten sind Salomonische Verschlingungen intrinsisch chiral. [281] Aufbauend auf ihren Au-Catenansystemen [294] (Schema 79) beschrieben Puddephatt und Mitarbeiter die Bildung eines "zweifach umflochtenen" [2]Catenans (der Salomonischen Verschlingung 233-Au I ), die durch aurophile Wechselwirkungen angeordnet wurde. [295,297] …”

Various Synthetic Routes to a Gable‐Like Bis(porphyrin) Constructed on a 1,10‐Phenanthroline Chelate

“…Phenanthroline 3 was prepared by a two-step procedure from 1,10-phenanthroline as described by our group. [15] The final double Suzuki reaction involving 3 and 4 (2 equiv.) was performed under classical conditions to give 1 in 53 % yield after purification by column chromatography.…”