The enantioselective
transformation of ubiquitous C–H bonds
into valuable CO bonds offers an efficient synthetic approach
to construct carbonyl functionalized molecules. However, the grand
obstacles in the reaction are the selectivity issues and side reactions
under the harsh reaction conditions. In order to overcome the limits,
two Cu(I)-based MOFs {(NEt4)0.5[Cu3(TTPB)0.75(CN)0.5(H2O)]·H2O}
n
(1) and {[Cu2(TTPB)0.5]·DMF·2H2O}
n
(2) were synthesized (H4TTPB = 5,5′-(4′,5′-bis(4-(1H-tetrazol-5-yl)phenyl)-[1,1′:2′,1′′-terphenyl]-4,4′′-diyl)
bis(1H-tetrazole)) under hydrothermal conditions
with (triethylamine (TEA) and ethyldiisopropylamine (DIPEA) as structure-directing
agents, respectively. Of these, 1 shows an anionic three-dimensional
(3D) framework composed of two kinds of cagelike micropores with 7
× 17 Å and 10 × 17 Å, respectively. In comparison, 2 exhibits a 3D framework with open channels (14 × 8
Å). The stability studies showed that the crystallinity of 1 and 2 could remain in a series of organic solvents
(ethanol, N,N-dimethylformamide,
chloroform, dioxane, toluene) and acid and alkali aqueous solutions
(pH = 1–13) at room temperature for 48 h. 1 and 2 with coordinatively unsaturated Cu(I) sites were applied
as heterogeneous catalysts for the oxidation of arylacycloalkanes
in aqueous medium and exhibited excellent catalytic activities, selectivities,
and recyclabilities. Moreover, free-radical reaction mechanism and
reversible valence-tautomeric conversions of central copper were confirmed
during the process by control experiment.
Efficient strut-to-strut energy transfer (antenna behavior) was observed in the well-ordered donor–acceptor system. Color tuning, adjustment of gamut, and regulation of sensitivity can be realized by the judicious choice of the constitutions of MOFs.
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