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Static Modulation Wave of Arrays of Halogen Interactions Transduced to a Hierarchy of Nanoscale Change Stimuli of Crystalline Rotors Dynamics

Abstract : Here we present a study where what can be seen as a static modulation wave encompassing four successive arrays of interacting iodine atoms in cryst. 1,​4-​Bis((4'-​(iodoethynyl)​phenyl) ethynyl)​bicyclo[2,​2,​2]​octane rotors changes the structure from one-​half mol. to three-​and-​a-​half mols. in the asym. unit below a phase transition at 105 K.  The remarkable finding is that the total 1H spin-​lattice relaxation rate, T1-​1, of unprecedented complexity to date in mol. rotors, is the weighted sum of the relaxation rates of the four contributing rotors relaxation rates, each with distinguishable exchange frequencies reflecting Arrhenius parameters with different activation barriers (Ea) and attempt frequencies (τo-​1)​.  This allows us to show in tandem with rotor-​environment interaction energy calcns. how the dynamics of mol. rotors are able to decode structural information from their surroundings with remarkable nanoscale precision.
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Sergey Simonov, Leokadiya Zorina, Pawel Wzietek, Antonio Rodríguez-Fortea, Enric Canadell, et al.. Static Modulation Wave of Arrays of Halogen Interactions Transduced to a Hierarchy of Nanoscale Change Stimuli of Crystalline Rotors Dynamics. Nano Letters, American Chemical Society, 2018, 18 (6), pp.3780-3784. ⟨10.1021/acs.nanolett.8b00956⟩. ⟨hal-02564483⟩

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