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Coordination Sphere Flexibility Leads to Elastic Deformation in a One-Dimensional Coordination Polymer Crystal

Sajesh P. Thomas, Anna Worthy, Espen Z. Eikeland, Amy J. Thompson, Arnaud Grosjean, Kasper Tolborg, Lennard Krause, Kunihisa Sugimoto, Mark A. Spackman, John C. McMurtrie, Jack K. Clegg, Bo B. Iversen

2023Chemistry of Materials24 citationsDOI

Abstract

Coordination polymers exhibiting mechanical flexibility including elastic or plastic bending are rare. Here, we report an example of a mechanically flexible one-dimensional coordination polymer that shows elastic bending. Quantitative insights on the inter and intra-chain bonding as well as structural flexibility from a combination of techniques including variable temperature single crystal X-ray diffraction (XRD), high-pressure crystallography (ambient─15 GPa), synchrotron micro-XRD mapping of the bent crystal, and high-resolution synchrotron X-ray charge density analysis show that the helical coordination polymer behaves like a spring when subjected to external stimuli. Changes that occur with the variation of temperature, pressure, or bending, however, result in very different mechanistic changes. The exceptional coordination sphere flexibility rendered by the presence of Jahn–Teller distorted coordination bonds leads to the flexibility of the polymer.

Topics & Concepts

Bent molecular geometryMaterials scienceSynchrotronCoordination polymerCrystallographyCoordination spherePolymerFlexibility (engineering)BendingSingle crystalCoordination numberCrystal structureDeformation (meteorology)DiffractionChemical physicsCrystal (programming language)NanotechnologyComposite materialChemistryOpticsIonPhysicsComputer scienceOrganic chemistryProgramming languageMathematicsStatisticsMetal-Organic Frameworks: Synthesis and ApplicationsCrystallography and molecular interactionsMagnetism in coordination complexes