Triazolyl-Based Copper-Molybdate Hybrids: From Composition Space Diagram to Magnetism and Catalytic Performance
authors Senchyk, GA; Lysenko, AB; Babaryk, AA; Rusanov, EB; Krautscheid, H; Neves, P; Valente, AA; Goncalves, IS; Kramer, KW; Liu, SX; Decurtins, S; Domasevitch, KV
nationality International
journal INORGANIC CHEMISTRY
keywords TERT-BUTYL HYDROPEROXIDE; HYDROTHERMAL SYNTHESIS; COORDINATION POLYMERS; FUNCTIONALIZED ADAMANTANES; EFFICIENT OXIDATION; CRYSTAL-STRUCTURE; BUILDING-BLOCKS; COMPLEXES; SYSTEM; LIGANDS
abstract The multicomponent mixed-metal Cu-II/Mo-VI oxides/1,3-bis(1,2,4-triazol-4-yl)adamantane (tr(2)ad) system was thoroughly studied employing a compositional diagram approach. The concept allowed us to prepare three layered copper-molybdate hybrid solids [Cu-2(II)(tr(2)ad)(4)](Mo8O26) (1), [Cu-4(II)(mu(4)-O)(tr(2)ad)(2)(MoO4)(3)]center dot 7.5H(2)O (2), and [Cu-2(I)(tr(2)ad)(2)](Mo2O7). H2O (3), and to elucidate the relationship between initial reagent concentration/stoichiometry and the stability of the resultant structural motifs. Compounds 1 and 2 were found to dominate throughout a wide crystallization range of the concentration triangle, whereas compound 3 was formed by redox processes in the narrow crystallization area having a high excess of Cu(OAc)(2)center dot H2O. Independent experiments carried out with Cu(OAc)(2) and (NH4)(6)Mo7O24 in the absence of tr(2)ad, under the same conditions, revealed the formation of low-valent and bimetallic oxides, including Cu2O, MoO2, Cu(Mo3O10)center dot H2O, and Cu-3(MoO4)(2)(OH)(2). Compounds 1 and 2 show high thermal and chemical stability as examined as catalysts in the epoxidation of cis-cyclooctene and the oxidation of benzyl alcohol (BzOH) with different types of oxidants. The oxidation reaction of BzOH using tert-butyl hydroperoidde (TBHP) as the oxidant, in the presence of 1 or 2, led to benzaldehyde and benzoic acid (PhCO2H), with the latter being formed in up to 90% yield at 24 h. The results suggest that 1 and 2 may be favorable heterogeneous catalysts for the synthesis of PhCO2H. Whereas compound 1 only reveals a weak ferromagnetic coupling between neighboring Cu-II centers (J = 0.41 cm(-1)), compound 2 shows distinct intraduster antiferromagnetic exchange interactions (J = 29.9 cm(-1), J' = 25.7 cm(-1)), which consequently results in a diamagnetic ground state.
publisher AMER CHEMICAL SOC
issn 0020-1669
year published 2014
volume 53
issue 19
beginning page 10112
ending page 10121
digital object identifier (doi) 10.1021/ic5009736
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000342856800023
link 25207750
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journal impact factor 4.825
5 year journal impact factor 4.501
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