We demonstrate herein a facile strategy
to engineer versatile catalytically
active coordination interspace in the same primitive metal–organic
framework (MOF) for variable heterogeneous catalysis. Different functional
ligands can be reversibly inserted into and removed from proto-LIFM-28 individually or successively to bring in single or binary
catalytic sites for specific reactions and switch the parent MOF to
multipurpose catalysts. Alcohol-oxidation, Knoevenagel-condensation,
click, acetal, and Baylis–Hillman reactions are achievable
through simple exchange of a single catalytic spacer, while sequential
or stepwise reactions are designable via selective combination of
two catalytic spacers with different functionalities, thus making proto-LIFM-28 a multivariate MOF for multiuse and economic
catalysis.
We report a practical approach, the first of its kind, to construct nanoscale UiO-type metal-organic framework (Mi-UiO-66 and Mi-UiO-67) fluorescent probes for the detection of Cys and GSH. They showed high sensitivity (10(-11) M) and selectivity for Cys and GSH, and their fluorescence imaging of Cys and GSH in living cells was well demonstrated.
In multiphoton excited fluorescence (MPEF), highenergy upconversion emission is obtained from low-energy excitation by absorbance of two or more photons simultaneously.I napressure-induced fluorochromic process,t he emission energy is switched by outer pressure stimuli. Now,five metal-organic frameworks containing the same ligand with simultaneous multiphoton absorption and pressure-induced fluorochromic attributes were studied. One-, two-, and threephoton excited fluorescence (1/2/3PEF) can be achieved in the frameworks,w hich exhibit pressure-induced blue-to-yellow fluorochromism. The performances are closely dependent with the topologies,f lexibilities,a nd packing states of the frameworks and chromophores therein. The multiphoton upconversion performance can be intensified by pressure-related structural contraction. Over ten-fold increment in the 2PA active cross-section up to 2217 GM is achieved in pressed LIFM-114 compared with the 210 GM for pristine sample at 780 nm.
We transformed the hydrophilic metal–organic framework (MOF) UiO‐67 into hydrophobic UiO‐67‐Rs (R=alkyl) by introducing alkyl chains into organic linkers, which not only protected hydrophilic Zr6O8 clusters to make the MOF interspace superoleophilic, but also led to a rough crystal surface beneficial for superhydrophobicity. The UiO‐67‐Rs displayed high acid, base, and water stability, and long alkyl chains offered better hydrophobicity. Good hydrophobicity/oleophilicity were also possible with mixed‐ligand MOFs containing metal‐binding ligands. Thus, a (super)hydrophobic MOF catalyst loaded with Pd centers efficiently catalyzed Sonogashira reactions in water at ambient temperature. Studies of the hydrophobic effects of the coordination interspace and the outer surface suggest a simple de novo strategy for the synthesis of superhydrophobic MOFs that combine surface roughness and low surface energy. Such MOFs have potential for environmentally friendly catalysis and water purification.
A zirconium-based
metal–organic framework (Zr-MOF) with
a 2-fold catenated breathing structure is designed, whose framework
contracts in a similarly consecutive manner responsive to solvent
(S), temperature (T), or pressure
(P). As a result, photoluminescence color tuning
(PLCT) can be achieved progressively from blue to yellow, via S, T, or P pathways, leading
to multiple PL states with memory nature. Based on this, a 3D PLCT
coordinate system is established. Along each stimulation pathway,
the starting, ending, and multiple intermediate PLCT states can be
recognized and plotted on the S, T, and P axes of the coordinate system. Furthermore,
multiplexing node-transfer pathways are programmed among the axes,
in which two or three kinds of outer stimuli (S/T/P) are implemented successively and alternatively,
leading to various stages of PL states. This multiplexing approach
provides a new strategy to control and utilize the multiresponsiveness
of PL-MOFs for intriguing applications such as composite nonvolatile
data storage and so on.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.