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Geometric isomerism in mechanically interlocked systems — which arises when the axle of a mechanically interlocked molecule is oriented, and the macrocyclic component is facially dissymmetric — can provide enhanced functionality for directional transport and polymerization catalysis. We now introduce a kinetically controlled strategy to control geometric isomerism in [2]rotaxanes. Our synthesis provides the major geometric isomer with high selectivity, broadening synthetic access to such interlocked structures. Starting from a readily accessible [2]rotaxane with a symmetrical axle, one of the two stoppers is activated selectively for stopper exchange by the substituents on the ring component. High selectivities are achieved in these reactions, based on coupling the selective formation reactions leading to the major products with inversely selective depletion reactions for the minor products. Specifically, in our reaction system, the desired (major) product forms faster in the first step, while the undesired (minor) product subsequently reacts away faster in the second step. Quantitative 1H NMR data, fit to a detailed kinetic model, demonstrates that this effect (which is conceptually closely related to minor enantiomer recycling and related processes) can significantly improve the intrinsic selectivity of the reactions. Our results serve as proof of principle for how multiple selective reaction steps can work together to enhance the stereoselectivity of synthetic processes forming complex mechanically interlocked molecules. 

Covalently linked molecular cages can provide significant advantages (including, but not limited to enhanced thermal and chemical stability) over metal-linked coordination cages. Yet, while large coordination cages can now be created routinely, it is still challenging to create chemically robust, covalently linked molecular cages with large internal cavities. This fundamental challenge has made it difficult, for example, to introduce endohedral functional groups into covalent cages to enhance their practical utility (e.g., for selective guest recognition or catalysis), since the cavities would have simply been filled up with such endohedral functional groups in most cases. Here we now report the synthesis of some of the largest known covalently linked molecular tetrahedra. Our new covalent cages all contain 12 peripheral functional groups, which keep them soluble. They are formed from a common vertex, which aligns the hydrazide functions required for the hydrazone linkages with atropisomerism. While we previously reported this vertex as a building block for the smallest member of our hydrazone-linked tetrahedra, our original synthesis was not feasible to be carried out on the larger scales required to successfully access the larger tetrahedra. To overcome this synthetic challenge, we now present an improved synthesis of our vertex, which only requires a single chromatographic step (compared to 3 chromatographic purification steps, which were needed for the initial synthesis). Our new synthetic route enabled us to create a whole family of molecular cages with increasing size (all linked with hydrolytically stable hydrazone bonds), with our largest covalent cage featuring p-quarterphenyl linkers and the ability to encapsulate a hypothetical sphere of approximately 3 nm in diameter. These results now open up the possibility to introduce functional groups required for selective recognition and catalysis into chemically robust covalent cages (without blocking the cavities of the covalent cages). 

Abstract We report a general synthetic route toward helical ladder polymers with varying spring constants, built with chirality‐assisted synthesis (CAS). Under tension and compression, these shape‐persistent structures do not unfold, but rather stretch and compress akin classical Hookean springs. Our synthesis is adaptable to helices with different pitch and diameter, which allowed us to investigate how molecular flexibility in solution depends on the exact geometry of the ladder polymers. Specifically, we showed with molecular dynamic simulations and by measuring the longitudinal¹H NMR relaxation times (T₁) for our polymers at different Larmor frequencies, that increasing the helix diameter leads to increased flexibility. Our results present initial design rules for tuning the mechanical properties of intrinsically helical ladder polymers in solution, which will help inspire a new class of robust, spring‐like molecular materials with varying mechanical properties.