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Helical Molecular Springs with Varying Spring Constants

Kyle E. Murphy, Kyle T. McKay, Mica Schenkelberg, Mona Sharafi, Olav Vestrheim, Monika Ivancic, Jianing Li, Severin T. Schneebeli

2022Angewandte Chemie International Edition15 citationsDOI

Abstract

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 longitudinal 1 H NMR relaxation times ( T 1 ) 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.

Topics & Concepts

Flexibility (engineering)Spring (device)PolymerTension (geology)Materials scienceHelix (gastropod)Relaxation (psychology)Molecular dynamicsChemical physicsCompression (physics)Composite materialPhysicsChemistryComputational chemistryThermodynamicsMathematicsSocial psychologyPsychologyEcologyStatisticsSnailBiologySynthesis and Properties of Aromatic CompoundsSupramolecular Chemistry and ComplexesSupramolecular Self-Assembly in Materials
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