Barium coordination polymers based on fluorinated and fluorine-free benzene-dicarboxylates: Mechanochemical synthesis and spectroscopic characterization

A series of new Ba-based coordination polymers (CPs) were mechanochemically synthesized by milling Ba-hydroxide samples with perfluorinated and fluorine-free benzene-dicarboxylic acids, including tetrafluoroisophthalic acid (H(2)mBDC-F-4), tetrafluorophthalic acid (H(2)oBDC-F-4), isophthalic acid (H(2)mBDC) and phthalic acid (H(2)oBDC). The new fluorinated CPs: [Ba(mBDC-F-4)center dot 0.5H(2)O] (1) and [Ba(oBDC-F-4)center dot 1.5H(2)O] (2) are compared to their nonfluorinated counterparts: [Ba(mBDC)center dot 2.5H(2)O] (3), and [Ba(oBDC)center dot 1H(2)O] (4). These materials are thoroughly characterized using powder X-ray diffraction. The products obtained by milling are all hydrated but vary in their water contents. Compositions and local structures are investigated by elemental analysis, thermal analysis, MAS NMR and attenuated total reflection-infrared spectroscopy. These materials exhibit high thermal stabilities but small surface areas that remain unchanged even after thermal treatments. (C) 2018 Elsevier Masson SAS. All rights reserved.