A simple and effective charge-assisted self-assembly process was developed to encapsulate a noble-metal-free polyoxometalate (POM) inside porous phosphorescent metal-organic framework (MOF) built from [Ru(bpy)3](2+)-derived dicarboxylate ligands Zr6(μ3-O)4(μ3-OH)4 secondary building units. Hierarchical organization of photosensitizing catalytic proton reduction components in such POM@MOF assembly enables fast multielectron injection the photoactive encapsulated redox-active POMs upon...

Abstract Metal–organic layers (MOLs) represent an emerging class of tunable and functionalizable two‐dimensional materials. In this work, the scalable solvothermal synthesis self‐supporting MOLs composed [Hf 6 O 4 (OH) (HCO 2 ) ] secondary building units (SBUs) benzene‐1,3,5‐tribenzoate (BTB) bridging ligands is reported. The MOL structures were directly imaged by TEM AFM, doped with 4′‐(4‐benzoate)‐(2,2′,2′′‐terpyridine)‐5,5′′‐dicarboxylate (TPY) before being coordinated iron centers to...

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant at metal-organic framework (MOF) nodes broad-scope organic transformations. The straightforward metalation MOF secondary building units (SBUs) with cobalt iron salts affords highly active reusable single-site solid range reactions, including chemoselective borylation, silylation amination benzylic C-H bonds, as well...

Metal-organic frameworks (MOFs) provide a tunable platform for hierarchically integrating multiple components to effect synergistic functions that cannot be achieved in solution. Here we report the encapsulation of Ni-containing polyoxometalate (POM) [Ni4 (H2 O)2 (PW9 O34 )2 ](10-) (Ni4 P2 ) into two highly stable and porous phosphorescent MOFs. The proximity Ni4 photosensitizers @MOF allows facile multi-electron transfer enable efficient visible-light-driven hydrogen evolution reaction...

We report here the synthesis of a robust and porous metal-organic framework (MOF), Zr12-TPDC, constructed from triphenyldicarboxylic acid (H2TPDC) an unprecedented Zr12 secondary building unit (SBU): Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6. The Zr12-SBU can be viewed as inorganic node dimerized two commonly observed Zr6 clusters via six μ2-OH groups. metalation Zr12-TPDC SBUs with CoCl2 followed by treatment NaBEt3H afforded highly active reusable solid Zr12-TPDC-Co catalyst for hydrogenation...

We report here the synthesis of robust and porous metal–organic frameworks (MOFs), M-MTBC (M = Zr or Hf), constructed from tetrahedral linker methane-tetrakis(p-biphenylcarboxylate) (MTBC) two types secondary building units (SBUs): cubic M8(μ2-O)8(μ2-OH)4 octahedral M6(μ3-O)4(μ3-OH)4. While M6-SBU is isostructural with 12-connected SBUs UiO-type MOFs, M8-SBU composed eight MIV ions in a fashion linked by μ2-oxo four μ2-OH groups. The metalation Zr-MTBC CoCl2, followed treatment NaBEt3H,...

We report the rational design of metal–organic layers (MOLs) that are built from [Hf6O4(OH)4(HCO2)6] secondary building units (SBUs) and Ir[bpy(ppy)2]+- or [Ru(bpy)3]2+-derived tricarboxylate ligands (Hf-BPY-Ir Hf-BPY-Ru; bpy=2,2′-bipyridine, ppy=2-phenylpyridine) their applications in X-ray-induced photodynamic therapy (X-PDT) colon cancer. Heavy Hf atoms SBUs efficiently absorb X-rays transfer energy to Ir[bpy(ppy)2]+ [Ru(bpy)3]2+ moieties induce PDT by generating reactive oxygen species...

Despite adopting diverse strategies and fabrication methods to prevent biofilm formation, the existing sophisticated for sole wettable or smart surfaces their unsatisfactory anti-adhesive durability need be improved practical applications.

Abstract Microenvironments in enzymes play crucial roles controlling the activities and selectivities of reaction centers. Herein we report tuning catalytic microenvironments metal–organic layers (MOLs), a two‐dimensional version frameworks (MOFs) with thickness down to monolayer, control product selectivities. By modifying secondary building units (SBUs) MOLs monocarboxylic acids, such as gluconic acid, changed hydrophobicity/hydrophilicity around active sites fine‐tuned selectivity...

We have designed a strategy for postsynthesis installation of the β-diketiminate (NacNac) functionality in metal–organic framework (MOF) UiO-topology. Metalation NacNac-MOF (I) with earth-abundant metal salts afforded desired MOF-supported NacNac-M complexes (M = Fe, Cu, and Co) coordination environments established by detailed EXAFS studies. The NacNac-Fe-MOF catalyst, I•Fe(Me), efficiently catalyzed challenging intramolecular sp3 C–H amination series alkyl azides to afford α-substituted...

The dimensionality dependency of resonance energy transfer is great interest due to its importance in understanding on cell membranes and low-dimension nanostructures. Light harvesting two-dimensional metal–organic layers (2D-MOLs) three-dimensional frameworks (3D-MOFs) provide comparative models study such dependence with molecular accuracy. Here we report the construction 2D-MOLs 3D-MOFs from a donor ligand 4,4′,4″-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE) doped acceptor...

Molecular iridium catalysts immobilized in metal–organic frameworks (MOFs) were positioned the condensing chamber of a Soxhlet extractor for efficient CO2 hydrogenation. Droplets hot water seeped through MOF catalyst to create dynamic gas/liquid interfaces which maximize contact CO2, H2, H2O, and achieve high turnover frequency 410 h–1 under atmospheric pressure at 85 °C. H/D kinetic isotope effect measurements density functional theory calculations revealed concerted proton–hydride transfer...

Metal–organic frameworks (MOFs) with light-harvesting building blocks designed to mimic photosynthetic chromophore arrays in green plants provide an excellent platform study exciton transport networks well-defined structures. A step-by-step random hopping model made of the elementary steps energy transfer between only nearest neighbors is usually used describe dynamics. Although such a neighbor approximation valid describing triplet states via Dexter mechanism, we found it inadequate...

XAFS investigation of polyamidoxime-bound uranyl reveals an adjacent μ²-oxo-bridged transition metal, suggesting new routes for adsorbent design in radionuclide separations.

We report here the design of BINAP-based metal–organic frameworks and their postsynthetic metalation with Rh complexes to afford highly active enantioselective single-site solid catalysts for asymmetric cyclization reactions 1,6-enynes. Robust, chiral, porous Zr-MOFs UiO topology, BINAP-MOF (I) or BINAP-dMOF (II), were prepared using purely BINAP-derived dicarboxylate linkers by mixing unfunctionalized linkers, respectively. Upon Rh(nbd)2BF4 [Rh(nbd)Cl]2/AgSbF6, MOF precatalysts I·Rh(BF4)...

Titania (TiO2) is widely used in the chemical industry as an efficacious catalyst support, benefiting from its unique strong metal-support interaction. Many proposals have been made to rationalize this effect at macroscopic level, yet underlying molecular mechanism not understood due presence of multiple catalytic species on TiO2 surface. This challenge can be addressed with metal-organic frameworks (MOFs) featuring well-defined metal oxo/hydroxo clusters for supporting single-site...

Mono(phosphine)–M (M–PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal–organic framework (MOF) exhibited excellent activity in the hydrosilylation ketones alkenes, hydrogenation C–H borylation arenes. The recyclable reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M–PR3 intermediates preventing deleterious disproportionation reactions/ligand exchanges catalytic cycles.

We report the stepwise and quantitative transformation of Zr6(μ3-O)4(μ3-OH)4(HCO2)6 nodes in Zr-BTC (MOF-808) to [Zr6(μ3-O)4(μ3-OH)4Cl12]6– ZrCl2-BTC, then organometallic [Zr6(μ3-O)4(μ3-OLi)4R12]6– ZrR2-BTC (R = CH2SiMe3 or Me). Activation ZrCl2-BTC with MMAO-12 generates ZrMe-BTC, which is an efficient catalyst for ethylene polymerization. ZrMe-BTC displays unusual electronic steric properties compared homogeneous Zr catalysts, possesses multimetallic active sites, produces...

We report the crystallization of homochiral polyoxometalate (POM) macroanions {CoSb6O4(H2O)3[Co(hmta)SbW8O31]3}15- (1, hmta = hexamethylenetetramine) via counter cation-mediated chiral symmetry breaking and asymmetric autocatalytic processes. In presence low Co2+ concentrations both Δ- Λ-enantiomers 1 formed in reaction, crystallizing into racemic crystal rac-1. At a high concentration, polyoxoanion enantiomers showed level recognition H-bonding interactions to crystallize enantiopure...

Metal–organic layers stabilize Fe^II or Co^II-terpyridine diradical complexes to catalyze alkylazide C_sp3–H amination and benzylic C–H borylation, respectively.

Abstract A series of porous twofold interpenetrated In‐Co III (porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration terminal alkynes. The interpenetrating structure brings adjacent Co (porphyrins) two networks parallel to each other with a distance about 8.8 Å, an ideal simultaneous activation both substrates alkyne reactions. As result, MOFs exhibit much higher (up 38 times)...

We report the stepwise, quantitative transformation of CeIV6(μ3-O)4(μ3-OH)4(OH)6(OH2)6 nodes in a new Ce-BTC (BTC = trimesic acid) metal–organic framework (MOF) into first CeIII6(μ3-O)4(μ3-OLi)4(H)6(THF)6Li6 metal-hydride that effectively catalyze hydroboration and hydrophosphination reactions. CeH-BTC displays low steric hindrance electron density compared to homogeneous organolanthanide catalysts, which likely accounts for unique 1,4-regioselectivity pyridine derivatives. MOF can thus be...

The first chiral rhodium-diene-based metal–organic frameworks are highly active and enantioselective catalysts for C–C bond formation reactions.

Abstract We report the rational design of metal–organic layers (MOLs) that are built from [Hf 6 O 4 (OH) (HCO 2 ) ] secondary building units (SBUs) and Ir[bpy(ppy) + ‐ or [Ru(bpy) 3 2+ ‐derived tricarboxylate ligands (Hf‐BPY‐Ir Hf‐BPY‐Ru; bpy=2,2′‐bipyridine, ppy=2‐phenylpyridine) their applications in X‐ray‐induced photodynamic therapy (X‐PDT) colon cancer. Heavy Hf atoms SBUs efficiently absorb X‐rays transfer energy to moieties induce PDT by generating reactive oxygen species (ROS). The...

Abstract Metal–organic layers (MOLs) represent an emerging class of tunable and functionalizable two‐dimensional materials. In this work, the scalable solvothermal synthesis self‐supporting MOLs composed [Hf 6 O 4 (OH) (HCO 2 ) ] secondary building units (SBUs) benzene‐1,3,5‐tribenzoate (BTB) bridging ligands is reported. The MOL structures were directly imaged by TEM AFM, doped with 4′‐(4‐benzoate)‐(2,2′,2′′‐terpyridine)‐5,5′′‐dicarboxylate (TPY) before being coordinated iron centers to...