The synthesis of nano-sized particles of NU-1000 (length from 75 nm to 1200 nm) and PCN-222/MOF-545 (length from 350 nm to 900 nm) is reported. The catalytic hydrolysis of methyl paraoxon was investigated as a function of NU-1000 crystallite size and a significant enhancement in the rate was observed for the nano-sized crystals compared to microcrystals.
A fullerene-based photosensitizer is incorporated postsynthetically into a Zr -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11 min.
We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with a pore volume of 1.53 ccg(-1) and Brunauer-Emmett-Teller (BET) surface area of 4020 m(2) g(-1) ; to our knowledge, currently the highest published for Zr-based MOFs. CH4 /CO2 /H2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g(-1) , which corresponds to 43 g L(-1) . The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 vSTP /v and 0.27 g g(-1) , respectively.
Intentional incorporation of defect sites functionalized with free carboxylic acid groups was achieved in a paddlewheel-based metal-organic framework (MOF) of rht topology, NU-125. Solvent-assisted linker exchange (SALE) performed on a mixed-linker derivative of NU-125 containing isophthalate (IPA) linkers (NU-125-IPA) led to the selective replacement of the IPA linkers in the framework with a conjugate base of trimesic acid (H3BTC). Only two of the three carboxylic acid moieties offered by H3BTC coordinate to the Cu2 centers in the MOF, yielding a rare example of a MOF decorated with free -COOH groups. The presence of the -COOH groups was confirmed by diffuse reflectance infrared Fourier-transformed spectroscopy (DRIFTS); moreover, these groups were found to be available for postsynthesis elaboration (selective monoester formation). This work constitutes an example of the use of SALE to obtain otherwise challenging-to-synthesize MOFs. The resulting MOF, in turn, can serve as a platform for accomplishing selective organic transformations, in this case, exclusive monoesterification of trimesic acid.
The compound HC(SiMe 3 ) 2 (SiMe 2 C 5 H 4 N-2), 1, reacts with methyllithium in THF to give a good yield of the lithium derivative Li{C(SiMe 3 ) 2 (SiMe 2 C 5 H 4 N-2)}, which has been isolated as a molecular THF adduct 2. This reacts (a) with KO t Bu to give K{C(SiMe 3 ) 2 (SiMe 2 C 5 H 4 N-2)}, 3, which crystallizes in a solvent-free ionic lattice, (b) with MgBr 2 to give the Grignard reagent Mg(THF)Br{C(SiMe 3 ) 2 (SiMe 2 C 5 H 4 N-2)}, 4, and (c) with CrCl 2 to give Cr{C(SiMe 3 ) 2 -(SiMe 2 C 5 H 4 N-2)} 2 , 5, along with the halide-bridged Grignard reagent analogue [Cr(µ-Cl)-{C(SiMe 3 ) 2 (SiMe 2 C 5 H 4 N-2)}] 2 ‚THF, 6, which crystallizes in a lattice containing alternate THF-free molecules (6a) and molecules (6b) with coordinated THF. The reactions of 2 with MnCl 2 and CoBr 2 give the halide-bridged ate complexes [Li(THF) 3 (µ-Cl)MnCl{C(SiMe 3 ) 2 -(SiMe 2 C 5 H 4 N-2)}], 7, and [Li(THF) 2 (µ-Br) 2 Co{C(SiMe 3 ) 2 (SiMe 2 C 5 H 4 N-2)}], 8, respectively.
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