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Issue 40, 2017
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Solid-state dynamics and single-crystal to single-crystal structural transformations in octakis(3-chloropropyl)octasilsesquioxane and octavinyloctasilsesquioxane

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Abstract

Reactive octahedral silsesquioxanes of rod-like [octakis(3-chloropropyl)octasilsesquioxane – T8(CH2CH2CH2Cl)8] and spherical [octavinyloctasilsesquioxane – T8(CH[double bond, length as m-dash]CH2)8] structure can undergo reversible thermally induced phase transitions in the solid state. The phase behaviour has been studied with differential scanning calorimetry (DSC, including temperature modulated DSC), X-ray diffraction, dielectric relaxation spectroscopy (DRS), and nuclear magnetic resonance spectroscopy in the solid state (SS NMR), as well as positron annihilation lifetime spectroscopy (PALS) and polarized optical microscopy (POM). The mechanisms involving fitting the molecules into most symmetrical crystal lattices vary for species of different structure. Thermal energy can be used to expand the crystal lattice leading to thermochromism in the case of T8(CH[double bond, length as m-dash]CH2)8 or conversely to an unusual negative thermal expansion of crystals of T8(CH2CH2CH2Cl)8 that results in their self-actuation. The complex behaviour is reflected in unusual changes in the capacitance and fractional free volume of the material. These phenomena can be used for molecular design of advanced well-defined hybrid materials capable of reversible thermally induced structural transformations. The findings present a new perspective for POSS-based flexible metal–organic frameworks (MOF) of cooperative structural transformability via entropy-based translational sub-net sliding.

Graphical abstract: Solid-state dynamics and single-crystal to single-crystal structural transformations in octakis(3-chloropropyl)octasilsesquioxane and octavinyloctasilsesquioxane

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Publication details

The article was received on 02 Aug 2017, accepted on 11 Sep 2017 and first published on 18 Sep 2017


Article type: Paper
DOI: 10.1039/C7CP05233B
Citation: Phys. Chem. Chem. Phys., 2017,19, 27516-27529
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    Solid-state dynamics and single-crystal to single-crystal structural transformations in octakis(3-chloropropyl)octasilsesquioxane and octavinyloctasilsesquioxane

    A. Kowalewska, M. Nowacka, M. Włodarska, B. Zgardzińska, R. Zaleski, M. Oszajca, J. Krajenta and S. Kaźmierski, Phys. Chem. Chem. Phys., 2017, 19, 27516
    DOI: 10.1039/C7CP05233B

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