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Controlled SBU Approaches to Isoreticular Metal‐Organic Framework Ruthenium‐Analogues of HKUST‐1
Author(s) -
Zhang Wenhua,
Kozachuk Olesia,
Medishetty Raghavender,
Schneemann Andreas,
Wagner Ralph,
Khaletskaya Kira,
Epp Konstantin,
Fischer Roland A.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500478
Subject(s) - chemistry , isostructural , ruthenium , metal organic framework , powder diffraction , crystallography , x ray absorption spectroscopy , valence (chemistry) , molecule , thermogravimetric analysis , carboxylate , metal , sorption , alkyl , inorganic chemistry , stereochemistry , absorption spectroscopy , crystal structure , organic chemistry , adsorption , catalysis , physics , quantum mechanics
A controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal‐organic frameworks (MOFs) of the general formula [Ru 3 (BTC) 2 X x ] · G g (BTC = 1,3,5‐benzenetricarboxylate; X = counter‐anion, G = guest molecules) which are structural analogues of [M 3 (BTC) 2 ] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru 2 (OOCR) 4 X] and [Ru 2 (OOCCH 3 ) 4 ]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl – ) and weakly coordinating Y ([BF 4 ] – or [BPh 4 ] – ) as well as the alkyl groups at the carboxylate ligand [R = CH 3 or C(CH 3 ) 3 ] were utilized. Four phase‐pure Ru‐MOFs were obtained: [Ru 3 (BTC) 2 Cl 0.5 (OH)] · (AcOH) 1.5 ( 1 ), [Ru 3 (BTC) 2 Cl 1.2 (OH) 0.3 ] · (H 3 BTC) 0.15 (AcOH) 2.4 (PivOH) 0.45 ( 2 ), [Ru 3 (BTC) 2 F 0.5 (OH)] · (AcOH) 1.0 ( 3 ) and [Ru 3 (BTC) 2 (OH) 1.5 ] · (H 3 BTC) 0.5 · (AcOH) 1.4 ( 4 ) {AcOH = CH 3 COOH, PivOH = (CH 3 ) 3 CCOOH}. The series of characterization data support the analytical composition and isostructural nature of 1 – 4 , i.e. powder X‐ray diffraction (PXRD), IR‐ and 1 H‐NMR spectroscopy, thermal gravimetric analysis (TGA) and N 2 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.