Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 17, Issue 50, Pages 14258-14266Publisher
WILEY-BLACKWELL
DOI: 10.1002/chem.201102026
Keywords
bioinorganic chemistry; bio-inspired catalysis; enzyme models; mesoporous silica; surface grafting
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Funding
- National Science Foundation of China [21003050, 20890124]
- Science and Technology Commission of Shanghai [10ZR1410500, 08DZ2273300]
- Fundamental Research Funds for the Central Universities
- French Ministry of Education
- Mobilite Internationale Rhone-Alpes (MIRA)
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Following the structural concept of copper-containing proteins in which dinuclear copper centers are connected by hydroxide bridging ligands, a bidentate copper(II) complex has been incorporated into nano-confined MCM-41 silica by a multistep sequential grafting technique. Characterization by a combination of EPR spectroscopy, X-ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, IR spectroscopy, and solid-state (13)C and (29)Si cross-polarization magic-angle spinning (CP-MAS) NMR suggests that dinuclear Cu complexes are bridged by hydroxide and other counterions (chloride or perchlorate ions), similar to the situation for EPR-undetectable [Cu(II)center dot center dot center dot Cu(II)] dimer analogues in biological systems. More importantly, a dynamic mononuclear-dinuclear equilibrium between different coordination modes of copper is observed, which strongly depends on the nature of the counterions (Cl(-) or ClO(4)(-)) in the copper precursor and the pore size of the silica matrix (the so-called confinement effect). A proton-transfer mechanism within the hydrogen-bonding network is suggested to explain the dynamic nature of the dinuclear copper complex supported on the MCM-41 silica.
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