Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 117, Issue 11, Pages 5658-5666Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp3056366
Keywords
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Funding
- German Research Foundation (DFG) through the Research Centre [SFB558]
- Ruhr University Research School at Bochum
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The mixed-valence metal-organic framework [Ru-3(II,III)-(btc)(2)Cl-1.5] (Ru-MOF) was synthesized by the controlled SBU approach and characterized by combined powder XRD, XPS, and FTIR methods. The interaction of CO molecules with Ru-MOF was studied by a novel instrumentation for ultra-high-vacuum (UHV) FTIR spectroscopy. The high-quality IR data demonstrate the presence of two different CO species within the framework: a strongly bonded CO showing a low-lying band at 2137 cm(-1) and a second CO species at 2171 cm(-1) with a lower binding energy. It was found that these IR bands cannot be assigned in a straightforward manner to CO molecules adsorbed on the coordinatively unsaturated Ru-II site (CUS) and Ru-III site connected to an additional Cl- ion for charge compensation. The accurate DFT calculations reveal that the structural and electronic properties of the mixed-valence Ru-MOF are much more complex than expected. One of the Cl- counterions could be transferred to a neighboring paddle-wheel, forming an anionic SBU blocked by two Cl- counterions, whereas the other positively charged paddle-wheel with a Ru-2(II,III) dimer exposes two free CUS, which can bind two CO molecules with different frequencies and binding energies.
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