Polyyne [3]Rotaxanes: Synthesis via Dicobalt Carbonyl Complexes and Enhanced Stability. (20th January 2022)

• Record Type: Journal Article
• Authors: Patrick, Connor W.; Woods, Joseph F.; Gawel, Przemyslaw; Otteson, Claire E.; Thompson, Amber L.; Claridge, Tim D. W.; Jasti, Ramesh; Anderson, Harry L.
• Is Part Of: Angewandte Chemie. Volume 134:Number 10(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-20
• Subjects: Rotaxanes -- Acetylene -- Polyynes -- Thermal Stability -- Template-Directed Synthesis; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202116897
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: New strategies for synthesizing polyyne polyrotaxanes are being developed as an approach to stable carbyne "insulated molecular wires". Here we report an active metal template route to polyyne [3]rotaxanes, using dicobalt carbonyl masked alkyne equivalents. We synthesized two [3]rotaxanes, both with the same C28 polyyne dumbbell component, one with a phenanthroline‐based macrocycle and one using a 2, 6‐pyridyl cycloparaphenylene nanohoop. The thermal stabilities of the two rotaxanes were compared with that of the naked polyyne dumbbell in decalin at 80 °C, and the nanohoop rotaxane was found to be 4.5 times more stable. Abstract : Cobalt carbonyl complexes have been used as temporary masking group, and temporary stoppers, in the synthesis of polyyne [3]rotaxanes with two macrocycles threaded on a C28 thread. Comparison of the thermal stability of two [3]rotaxanes with different threaded macrocycles shows that the 2, 6‐pyridyl cycloparaphenylene nanohoop effectively stabilizes the polyyne chain.