Postsynthetic ligand and metal ion exchange (PSE) processes are shown to readily occur in several "inert" metal-organic frameworks (MOFs), including zeolitic imidazolate (ZIFs). Ligand can between solid samples, as was demonstrated under relatively mild conditions with two robust, topologically distinct MOFs, MIL-53(Al) MIL-68(In). Interestingly, PSE is not observed MIL-101(Cr), which attributed the kinetic inertness of Cr(III) ion. In addition exchange, (cation) also studied intact MOF...

A molecular proton reduction catalyst [FeFe](dcbdt)(CO)6 (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal–organic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails produce the functionalized MOF. integrity of organometallic site within MOF demonstrated variety techniques, including X-ray absorption...

A manganese bipyridine complex, Mn(bpydc)(CO)3Br (bpydc = 5,5′-dicarboxylate-2,2′-bipyridine), has been incorporated into a highly robust Zr(IV)-based metal–organic framework (MOF) for use as CO2 reduction photocatalyst. In conjunction with [Ru(dmb)3]2+ (dmb 4,4′-dimethyl-2,2′-bipyridine) photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) sacrificial reductant, Mn-incorporated MOFs efficiently catalyze to formate in DMF/triethanolamine under visible-light irradiation. The...

An isolated metal-monocatecholato moiety has been achieved in a highly robust metal-organic framework (MOF) by two fundamentally different postsynthetic strategies: deprotection (PSD) and exchange (PSE). Compared with PSD, PSE proved to be more facile efficient functionalization approach access MOFs that could not directly synthesized under solvothermal conditions. Metalation of the catechol functionality residing resulted unprecedented Fe-monocatecholato Cr-monocatecholato species, which...

We report the synthesis and characterization of two Ag(I)/Cu(I)-based cationic metal-organic frameworks their application in both heterogeneous catalysis anion exchange. The Cu(I)-based material was designed from our previously reported Ag(I) topology. Both structures consist layers with pi-pi stacked chains alternating metal 4,4'-bipyridine. Alpha,omega-alkanedisulfonate serves as an anionic template, electrostatically bonding to layers. Due weak interaction between sulfonate template...

We describe a new methodology to the selective trapping of priority pollutants that occur inherently as oxo-anions (e.g., perchlorate, chromate, arsenate, pertechnetate, etc.) or organic anions salicylate, pharmaceuticals, and their metabolites, which are often chlorinated into potentially more harmful compounds). The typical approach is exchange cationic hosts such resins layered double hydroxides. Both capacity selectivity limited by equilibrium process moreover subject interference, e.g....

The incorporation of 2,3-dimercaptoterephthalate (thiocatecholate, tcat) into a highly robust UiO-type metal-organic framework (MOF) has been achieved via postsynthetic exchange (PSE). anionic, electron-donating thiocatecholato motif provides an excellent platform to obtain site-isolated and coordinatively unsaturated soft metal sites in MOF architecture. Metalation the thiocatechol group with palladium affords unprecedented Pd-mono(thiocatecholato) moieties within these MOFs. Importantly,...

Herein, we report a general postsynthetic exchange (PSE) approach to introduce redox-active transition metal, specifically Mn(II), into "inert" zeolitic imidazolate frameworks (ZIFs), subclass of metal–organic (MOFs). It is shown that metal ion PSE occurs in ZIF-71 (RHO topology) and ZIF-8 (SOD under ambient conditions. The exchanged ZIFs are the first porous, Mn(II)-based rare example with two centers single lattice. Exchanged materials characterized by scanning electron microscopy-energy...

We report two synthetic approaches to prepare a highly crystalline Zr(IV)-based metal-organic framework (MOF) containing open 2,2'-bipyridine (bpy) chelating sites. The resulting UiO-67-bpydc readily forms complexes with PdCl2 produce MOF that exhibits efficient and recyclable catalytic activity for the Suzuki-Miyaura cross-coupling reaction.

We report a rare example of sulfonate-based metal–organic framework (MOF) possessing prototypical primitive-cubic topology, constructed with Jahn–Teller distorted Cu(II) centers and mixed-linker (organosulfonate N-donor) system. The inherent highly polar, permanent porosity contributes to the highest reported CO2 sorption properties date among organosulfonate-based MOFs, outperforming benchmark carboxylate MOF counterpart. Importantly, density functional theory calculations confirm that...

Abstract Ultrafine gold nanoclusters (Au‐NCs) are susceptible to migrate and aggregate, even in the porosity of many crystalline solids. N‐heterocyclic carbenes (NHCs) a class structurally diverse ligands for stabilization Au‐NCs homogeneous chemistry, showing catalytic reactivity CO 2 activation. Herein, first time, we demonstrate heterogeneous nucleation approach stabilize ultrasmall highly dispersed an NHC‐functionalized porous matrix. The sizes tunable from 1.3 nm 1.8 based on...

Hybrid metal halides are an emerging class of highly efficient photoluminescent (PL) materials. However, very few them show reversible on–off PL switching under external stimuli and have the potential to perform as next-generation intelligent materials with applications in cutting-edge photoelectric devices. Herein, we report single crystal-to-single crystal (SC–SC) structural transitions among three 0D hybrid antimony halides, namely, nonemissive α-[DHEP]SbCl5 (1), yellow-emissive...

Organolead halide hybrids have many promising attributes for photocatalysis, e.g. tunable bandgaps and excellent carrier transport, but their instability constraints render them vulnerable to polar molecules limit photocatalysis in moisture. Herein, we report the construction of metal-organic frameworks based on [Pb

Lead halide hybrids have shown great potentials in CO

A noninterpenetrated organosulfonate-based metal–organic framework (MOF) with a defective primitive–cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along the highest permanent porosity (∼43%) in sulfonate-MOFs, offer versatile platform for incorporation of alkynophilic Ag(I) sites. cyclic carboxylation alkyne molecules (e.g., propargyl alcohol and amine) into α-alkylidene carbonates oxazolidinones were catalyzed by use Ag(I)-embedded sulfonate-MOF under...

Metal–organic frameworks (MOFs) as electrocatalysis scaffolds are appealing due to the large concentration of catalytic units that can be assembled in three dimensions. To harness full potential these materials, charge transport redox catalysts within MOF has ensured. Herein, we report first electroactive with UiO/PIZOF topology (Zr(dcphOH-NDI)), i.e., one most widely used MOFs for catalyst incorporation, by using redox-active naphthalene diimide-based linkers (dcphOH-NDI). Hydroxyl groups...

We report the synthesis and characterization of a solid solution series cationic metal–organic materials with full compositional range from pure Co(II) to Zn(II) end-members. The consist [ZnxCo1–x(H2O)4(4,4′-bipy)2]2+ clusters that π–π stack into 2-D positively charged layers, metal ratio tunable by molar under hydrothermal conditions. interlamellar α,ω-alkanedisulfonate serves as an anionic template noncovalently interacts layers. weak interaction allows anion exchange for toxic oxometal...

We report a family of cationic lead halide layered materials, formulated as [Pb2 X2 ]2+ [- O2 C(CH)2 CO2- ] (X=F, Cl, Br), exhibiting pronounced broadband white-light emission in bulk form. These well-defined PbX-based structures achieve an external quantum efficiency high 11.8 %, which is comparable to the highest reported value (ca.9 %) for phosphors based on organolead perovskites. More importantly, our materials are ultrastable overcome air/moisture-sensitivity problems In contrast...

Metal-organic frameworks (MOFs) with isolated metal-monocatecholato groups have been synthesized via postsynthetic exchange (PSE) for CO2 reduction photocatalyst under visible light irradiation in the presence of 1-benzyl-1,4-dihydronicotinamide and triethanolamine. The Cr-monocatecholato species are more efficient than Ga-monocatecholato species.

A facile and efficient fabrication approach for homogeneous, crack-free UiO-66 films with exceptionally high crystallinity tunable thickness on a transparent conductive glass substrate is reported. Two functionalized species, catechol ligand Fe2 complex structural resemblance to the active site of [FeFe] hydrogenase, were introduced into MOF via postsynthetic exchange. Voltammetric studies show in thinner (2-5 μm) can be reduced electrochemically.

The secondary building units in metal-organic frameworks (MOFs) are commonly well-defined metal-oxo clusters or chains with very limited structural strain. Herein, the structurally deformable haloplumbate that often observed organolead halide perovskites have been successfully incorporated into MOFs. resultant materials a rare class of isoreticular MOFs exhibiting large Stokes-shifted broadband white-light emission, which is probably induced by self-trapped excitons from electron-phonon...

The reported metal-organic framework (MOF) catalyst realizes CO2 to methanol transformation under ambient conditions. MOF is one rare example containing metal-free N-heterocyclic carbene (NHC) moieties, which are installed using an in situ generation strategy involving the incorporation of imidazolium bromide based linker into by postsynthetic ligand exchange. Importantly, resultant NHC-functionalized first capable performing quantitative hydrogen transfer from silanes , thus achieving (>99...