Abstract:Concentration of the metallosupramolecular polymer precursors have a significant effect on the architecture and size of the resulting poly[n]catenanes formed via a ring closing metathesis step.
“…2 equiv., see ESI, Fig. S2 †) and the mixture was equilibrated for 1 day at 45 C. Aer equilibration, the 1 H-NMR spectrum simplied and, using previously published 1 H NMR spectra of doubly threaded metal-templated Bip complexes, [87][88][89] it is possible to assign each resonance peak to a given proton in the complex (Fig. 1 and 2b).…”
Section: Resultsmentioning
confidence: 99%
“…The presence of such upeld shied peaks imply these protons are in a more shielded environment, and would be consistent with an interlocked structure. [87][88][89] A MALDI-TOF MS spectrum (see ESI, Fig. S12 †) of the reaction mixture recorded aer 6 minutes in solution conrmed only the presence of 1 and 6, with no signals indicative of [3]rotaxane 7.…”
Section: Resultsmentioning
confidence: 99%
“…While a wide range of ligands have been explored to access mechanically interlocked structures, 72 the terdentate ligand, 2,6-bis(N-alkyl-benzimidazolyl)pyridine (Bip), has a number of attractive features including a exible and scalable synthesis combined with the ability to tailor its solubility by altering its N-alkyl moieties. 80 It has also been used to access metallosupramolecular assemblies and polymers, [81][82][83][84][85] [2]catenates, 86 [3]catenates, 87 and poly[n]catenanes 88,89 via metal ion coordination. As such, this study utilizes Bip/metal ion templating to access isolatable doubly threaded [3]rotaxanes (Fig.…”
Multiple metastable doubly threaded [3]rotaxanes using a large 46 atom ring were prepared and fully characterized. Varying the stopper group size gave a range of interlocked stabilities in CDCl3 from a half-life of <1 minute to ca. 6 months.
“…2 equiv., see ESI, Fig. S2 †) and the mixture was equilibrated for 1 day at 45 C. Aer equilibration, the 1 H-NMR spectrum simplied and, using previously published 1 H NMR spectra of doubly threaded metal-templated Bip complexes, [87][88][89] it is possible to assign each resonance peak to a given proton in the complex (Fig. 1 and 2b).…”
Section: Resultsmentioning
confidence: 99%
“…The presence of such upeld shied peaks imply these protons are in a more shielded environment, and would be consistent with an interlocked structure. [87][88][89] A MALDI-TOF MS spectrum (see ESI, Fig. S12 †) of the reaction mixture recorded aer 6 minutes in solution conrmed only the presence of 1 and 6, with no signals indicative of [3]rotaxane 7.…”
Section: Resultsmentioning
confidence: 99%
“…While a wide range of ligands have been explored to access mechanically interlocked structures, 72 the terdentate ligand, 2,6-bis(N-alkyl-benzimidazolyl)pyridine (Bip), has a number of attractive features including a exible and scalable synthesis combined with the ability to tailor its solubility by altering its N-alkyl moieties. 80 It has also been used to access metallosupramolecular assemblies and polymers, [81][82][83][84][85] [2]catenates, 86 [3]catenates, 87 and poly[n]catenanes 88,89 via metal ion coordination. As such, this study utilizes Bip/metal ion templating to access isolatable doubly threaded [3]rotaxanes (Fig.…”
Multiple metastable doubly threaded [3]rotaxanes using a large 46 atom ring were prepared and fully characterized. Varying the stopper group size gave a range of interlocked stabilities in CDCl3 from a half-life of <1 minute to ca. 6 months.
“…Data suggested that the MSP was present in both the linear and cyclic form, the ratio of which depends on the reaction concentration. 72 Ring closing the thread component in the MSP was achieved through olefin metathesis of its alkene tails resulting in a mixture that contains the metalated poly[ n ]catenanes. Removal of the metal ion yielded the desired poly[ n ]catenane 30 , along with some non-interlocked species.…”
Section: Methods Utilized For the Synthesis Of Polycatenanesmentioning
confidence: 99%
“…In these high concentration reactions, evidence from MALS suggests the presence of poly[n]catenanes with up 640 interlocked rings (1000 kg mol À1 ). 72 As a consequence of the metal ion templating employed in the synthesis of the poly[n]catenanes, 30 exhibits stimuli-responsive behaviour. When the ligand moieties in these catenanes are not complexed to metal ions, the rings are mobile; however, adding in the metal ions results in the reformation of the metal-ligand complexes and a locking in of the catenane units.…”
Section: Ring Closing As the Polymerization Stepmentioning
Polycatenanes are a class of polymers that contain interlocked rings. This review explores the different polycatenane architectures with a focus on their synthesis, properties, simulation, and modelling.
Poly[n]catenanes have exceptional mechanical bonding properties that give them tremendous potential for use in the development of molecular machines and soft materials. Synthesizing these compounds has, however, proven to be a formidable challenge. Herein, we describe a concise method for the construction of twisted polycatenanes. Our approach involves using preorganized double helicates as templates, linked crosswise in a linear fashion by either silver ions or triple bonds. By using this approach, we successfully synthesized twisted polycatenanes with both coordination and covalent bonding employing Ag(I) ions and ethynylene units, respectively, as the linkages and leveraging the same Ag(I)‐templated double helicate in both cases. Synthesis with Ag(I) ions formed a single‐crystalline one‐dimensional (1D) coordination poly[n]catenane, and synthesis using ethynylene units generated 1D fibers which self‐assembled with solvents to form a gel. Our results confirm the potential of multi‐stranded metallohelicates for creating sophisticated mechanically interlocked molecules and polymers, which could pave the way for exploration in the realms of molecular nanotopology and materials design.
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