Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1

Wenhua Zhang, Olesia Kozachuk, Raghavender Medishetty, Andreas Schneemann, Ralph Wagner, Kira Khaletskaya, Konstantin Epp, Roland A. Fischer

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Abstract

A controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter-anion, G = guest molecules) which are structural analogues of [M3(BTC)2] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru2(OOCR)4X] and [Ru2(OOCCH3)4]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl-) and weakly coordinating Y ([BF4]- or [BPh4]-) as well as the alkyl groups at the carboxylate ligand [R = CH3 or C(CH3)3] were utilized. Four phase-pure Ru-MOFs were obtained: [Ru3(BTC)2Cl0.5(OH)]·(AcOH)1.5 (1), [Ru3(BTC)2Cl1.2(OH)0.3]·(H3BTC)0.15(AcOH)2.4(PivOH)0.45 (2), [Ru3(BTC)2F0.5(OH)]·(AcOH)1.0 (3) and [Ru3(BTC)2(OH)1.5]·(H3BTC)0.5·(AcOH)1.4 (4) {AcOH = CH3COOH, PivOH = (CH3)3CCOOH}. The series of characterization data support the analytical composition and isostructural nature of 1-4, i.e. powder X-ray diffraction (PXRD), IR- and 1H-NMR spectroscopy, thermal gravimetric analysis (TGA) and N2 sorption were employed. The valence state of the Ru-sites were studied by X-ray absorption spectroscopy (XAS). The chosen precursors for CSA and optimized synthesis, work-up and activation protocols allowed improvement of the overall crystallinity, purity (i.e., residual solvent molecules) and surface area of the Ru-MOF materials. A controlled secondary building unit approach (CSA) was employed to obtain a series of isostructural ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5-benzenetricarboxylate; X = counter anion, G = guest molecules) which are analogues of [Cu3(BTC)2] (HKUST-1).

Original languageEnglish
Pages (from-to)3913-3920
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2015
Issue number23
DOIs
StatePublished - 1 Aug 2015
Externally publishedYes

Keywords

  • Coordinatively unsaturated metal sites
  • Metal-organic frameworks
  • Ruthenium

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