Isomerization and Selective Hydrogenation of Propyne: Screening of Metal-Organic Frameworks Modified by Atomic Layer Deposition.

Various metal oxide clusters upward of 8 atoms (Cu, Cd, Co, Fe, Ga, Mn, Mo, Ni, Sn, W, Zn, In, and Al) were incorporated into the pores of the metal-organic framework (MOF) NU-1000 via atomic layer deposition (ALD) and tested via high-throughput screening for catalytic isomerization and selective hydrogenation of propyne. Cu and Co were found to be the most active for propyne hydrogenation to propylene, and synergistic bimetallic combinations of Co and Zn, along with standalone Zn and Cd, were established as the most active for conversion to the isomerized product, propadiene. The combination of Co and Zn in NU-1000 diminished the propensity for full hydrogenation to propane as well as coking compared to its individual components. This study highlights the potential for high-throughput screening to survey monometallic and bimetallic cluster combinations that best affect the efficient transformation of small molecules, while discerning mechanistic differences in isomerization and hydrogenation by different metals.

The Synthesis Science of Targeted Vapor-Phase Metal-Organic Framework Postmodification.

The postmodification of metal organic frameworks (MOFs) affords exceedingly high surface area materials with precisely installed chemical features, which provide new opportunities for detailed structure-function correlation in the field of catalysis. Here, we significantly expand upon the number of vapor-phase postmodification processes reported to date through screening a library of atomic layer deposition (ALD) precursors, which span metals across the periodic table and which include ligands from four distinct precursor classes. With a large library of precursors and synthesis conditions, we discern trends in the compatibility of precursor classes for well-behaved ALD in MOFs (AIM) and identify challenges and solutions to more precise postsynthetic modification.

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant.

Amino-functionalized zirconium-based metal-organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH2 , where the amino groups reside near the node, compared to UiO-67-m-NH2 , where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents. The generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr6 -node active site and therefore increase the overall catalytic rates.

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

Supramolecular Explorations: Exhibiting the Extent of Extended Cationic Cyclophanes.

Acting as hosts, cationic cyclophanes, consisting of π-electron-poor bipyridinium units, are capable of entering into strong donor-acceptor interactions to form host-guest complexes with various guests when the size and electronic constitution are appropriately matched. A synthetic protocol has been developed that utilizes catalytic quantities of tetrabutylammonium iodide to make a wide variety of cationic pyridinium-based cyclophanes in a quick and easy manner. Members of this class of cationic cyclophanes with boxlike geometries, dubbed Ex(n)Boxm(4+) for short, have been prepared by altering a number of variables: (i) n, the number of "horizontal" p-phenylene spacers between adjoining pyridinium units, to modulate the "length" of the cavity; (ii) m, the number of "vertical" p-phenylene spacers, to modulate the "width" of the cavity; and (iii) the aromatic linkers, namely, 1,4-di- and 1,3,5-trisubstituted units for the construction of macrocycles (ExBoxes) and macrobicycles (ExCages), respectively. This Account serves as an exploration of the properties that emerge from these structural modifications of the pyridinium-based hosts, coupled with a call for further investigation into the wealth of properties inherent in this class of compounds. By variation of only the aforementioned components, the role of these cationic receptors covers ground that spans (i) synthetic methodology, (ii) extraction and sequestration, (iii) catalysis, (iv) molecular electronics, (v) physical organic chemistry, and (vi) supramolecular chemistry. Ex(1)Box(4+) (or simply ExBox(4+)) has been shown to be a multipurpose receptor capable of binding a wide range of polycyclic aromatic hydrocarbons (PAHs), while also being a suitable component in switchable mechanically interlocked molecules. Additionally, the electronic properties of some host-guest complexes allow the development of artificial photosystems. Ex(2)Box(4+) boasts the ability to bind both π-electron-rich and -poor aromatic guests in different binding sites located within the same cavity. ExBox2(4+) forms complexes with C60 in which discrete arrays of aligned fullerenes result in single cocrystals, leading to improved material conductivities. When the substitution pattern of the Ex(n)Box(4+) series is changed to 1,3,5-trisubstituted benzenoid cores, the hexacationic cagelike compound, termed ExCage(6+), exhibits different kinetics of complexation with guests of varying sizes-a veritable playground for physical organic chemists. The organization of functionality with respect to structure becomes valuable as the number of analogues continues to grow. With each of these minor structural modifications, a wealth of properties emerge, begging the question as to what discoveries await and what properties will be realized with the continued exploration of this area of supramolecular chemistry based on a unique class of receptor molecules.

Magnetic Control of MOF Crystal Orientation and Alignment.

Most metal-organic frameworks (MOFs) possess anisotropic properties, the full exploitation of which necessitates a general strategy for the controllable orientation of such MOF crystals. Current methods largely rely upon layer-by-layer MOF epitaxy or tuning of MOF crystal growth on appropriate substrates, yielding MOFs with fixed crystal orientations. Here, the dynamic magnetic alignment of different MOF crystals (NH2 -MIL-53(Al) and NU-1000) is shown. The MOFs were magnetized by electrostatic adsorption of iron oxide nanoparticles, dispersed in curable polymer resins (Formlabs 1+ clear resin/ Sylgard 184), magnetically oriented, and fixed by resin curing. The importance of crystal orientation on MOF functionality was demonstrated whereby magnetically aligned NU-1000/Sylgard 184 composite was excited with linearly polarized 405 nm light, affording an anisotropic fluorescence response dependent on the polarization angle of the excitation beam relative to NU-1000 crystal orientation.

Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition.

An efficient aerobic linear allylic C-H amination reaction is reported under palladium(II)/bis-sulfoxide/Brønsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with reduced Pd(II)/bis-sulfoxide catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant. Pd(II)/BQ π-acidic interactions have been invoked in various catalytic processes and are often considered beneficial in promoting reductive functionalizations. When such electrophilic activation for functionalization is not needed, however, BQ at high concentrations may compete with crucial ligand (bis-sulfoxide) binding and inhibit catalysis. Kinetic studies reveal an inverse relationship between the reaction rate and the concentration of BQ, suggesting that BQ is acting as a ligand for Pd(II) which results in an inhibitory effect on catalysis.

Non-Interpenetrated Metal-Organic Frameworks Based on Copper(II) Paddlewheel and Oligoparaxylene-Isophthalate Linkers: Synthesis, Structure, and Gas Adsorption.

Two metal-organic framework materials, MFM-130 and MFM-131 (MFM = Manchester Framework Material), have been synthesized using two oligoparaxylene (OPX) tetracarboxylate linkers containing four and five aromatic rings, respectively. Both fof-type non-interpenetrated networks contain Kagomé lattice layers comprising [Cu2(COO)4] paddlewheel units and isophthalates, which are pillared by the OPX linkers. Desolvated MFM-130, MFM-130a, shows permanent porosity (BET surface area of 2173 m(2)/g, pore volume of 1.0 cm(3)/g), high H2 storage capacity at 77 K (5.3 wt% at 20 bar and 2.2 wt% at 1 bar), and a higher CH4 adsorption uptake (163 cm(3)(STP)/cm(3) (35 bar and 298 K)) compared with its structural analogue, NOTT-103. MFM-130a also shows impressive selective adsorption of C2H2, C2H4, and C2H6 over CH4 at room temperature, indicating its potential for separation of C2 hydrocarbons from CH4. The single-crystal structure of MFM-131 confirms that the methyl substituents of the paraxylene units block the windows in the Kagomé lattice layer of the framework, effectively inhibiting network interpenetration in MFM-131. This situation is to be contrasted with that of the doubly interpenetrated oligophenylene analogue, NOTT-104. Calculation of the mechanical properties of these two MOFs confirms and explains the instability of MFM-131 upon desolvation in contrast to the behavior of MFM-130. The incorporation of paraxylene units, therefore, provides an efficient method for preventing network interpenetration as well as accessing new functional materials with modified and selective sorption properties for gas substrates.

Cooperative Reactivity in an Extended-Viologen-Based Cyclophane.

A tetracationic pyridinium-based cyclophane with a box-like geometry, incorporating two juxtaposed alkyne functions, has been synthesized. The triple bonds are reactive through cycloadditions toward dienes and azides, promoted by the electron-withdrawing nature of the pyridinium rings, as well as by the strain inherent in the cyclophane. The cycloadditions proceeded in high yields, with the cyclophane reacting faster than its acyclic analogue. While the cyclophane contains two reactive triple bonds, there is no evidence for a stable monofunctional intermediate-only starting material and the difunctional product have been detected by (1)H NMR spectroscopy. Molecular modeling of the energy landscape reveals a lower barrier for the kinetically favored second cycloaddition compared with the first one. This situation results in tandem cascading reactions within rigid cyclophanes, where reactions at a first triple bond induce increased reactivity at a distal second alkyne.

CD-MOF: A Versatile Separation Medium.

Porous metal-organic frameworks (MOFs) have been studied in the context of a wide variety of applications, particularly in relation to molecular storage and separation sciences. Recently, we reported a green, renewable framework material composed of γ-cyclodextrin (γ-CD) and alkali metal salts--namely, CD-MOF. This porous material has been shown to facilitate the separation of mixtures of alkylaromatic compounds, including the BTEX mixture (benzene, toluene, ethylbenzene, and the regioisomers of xylene), into their pure components, in both the liquid and gas phases, in an energy-efficient manner which could have implications for the petrochemical industry. Here, we report the ability of CD-MOF to separate a wide variety of mixtures, including ethylbenzene from styrene, haloaromatics, terpinenes, pinenes and other chiral compounds. CD-MOF retains saturated compounds to a greater extent than their unsaturated analogues. Also, the location of a double bond within a molecule influences its retention within the extended framework, as revealed in the case of the structural isomers of pinene and terpinine, where the isomers with exocyclic double bonds are more highly retained than those with endocyclic double bonds. The ability of CD-MOF to separate various mono- and disubstituted haloaromatic compounds appears to be controlled by both the size of the halogen substituents and the strength of the noncovalent bonding interactions between the analyte and the framework, an observation which has been confirmed by molecular simulations. Since CD-MOF is a homochiral framework, it is also able to resolve the enantiomers of chiral analytes, including those of limonene and 1-phenylethanol. These findings could lead to cheaper and easier-to-prepare stationary phases for HPLC separations when compared with other chiral stationary phases, such as CD-bonded silica particles.

An Exceptionally Stable Metal-Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation.

Molybdenum(VI) oxide was deposited on the Zr6 node of the mesoporous metal-organic framework NU-1000 via condensed-phase deposition where the MOF is simply submerged in the precursor solution, a process named solvothermal deposition in MOFs (SIM). Exposure to oxygen leads to a monodisperse, porous heterogeneous catalyst, named Mo-SIM, and its structure on the node was elucidated both computationally and spectroscopically. The catalytic activity of Mo-SIM was tested for the epoxidation of cyclohexene. Near-quantitative yields of cyclohexene oxide and the ring-opened 1,2-cyclohexanediol were observed, indicating activity significantly higher than that of molybdenum(VI) oxide powder and comparable to that of a zirconia-supported analogue (Mo-ZrO2) prepared in a similar fashion. Despite the well-known leaching problem of supported molybdenum catalysts (i.e., loss of Mo species thus causes deactivation), Mo-SIM demonstrated no loss in the metal loading before and after catalysis, and no molybdenum was detected in the reaction mixture. In contrast, Mo-ZrO2 led to significant leaching and close to 80 wt % loss of the active species. The stability of Mo-SIM was further confirmed computationally, with density functional theory calculations indicating that the dissociation of the molybdenum(VI) species from the node of NU-1000 is endergonic, corroborating the experimental data for the Mo-SIM material.

Ultrafast Two-Electron Transfer in a CdS Quantum Dot-Extended-Viologen Cyclophane Complex.

Time-resolved optical spectroscopies reveal multielectron transfer from the biexcitonic state of a CdS quantum dot to an adsorbed tetracationic compound cyclobis(4,4'-(1,4-phenylene) bipyridin-1-ium-1,4-phenylene-bis(methylene)) (ExBox(4+)) to form both the ExBox(3+•) and the doubly reduced ExBox(2(+•)) states from a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps. At higher excitation powers the second electron transfer takes ∼5 ps, which leads to a mixture of redox states of the acceptor ligand. The doubly reduced ExBox(2(+•)) state has a lifetime of ∼10 ns, while CdS(+•):ExBox(3+•) recombines with multiple time constants, the longest of which is ∼300 µs. The long-lived charge separation and ability to accumulate multiple charges on ExBox(4+) demonstrate the potential of the CdS:ExBox(4+) complex to serve as a platform for two-electron photocatalysis.

Design and Synthesis of a Water-Stable Anionic Uranium-Based Metal-Organic Framework (MOF) with Ultra Large Pores.

Ionic metal-organic frameworks (MOFs) are a subclass of porous materials that have the ability to incorporate different charged species in confined nanospace by ion-exchange. To date, however, very few examples combining mesoporosity and water stability have been realized in ionic MOF chemistry. Herein, we report the rational design and synthesis of a water-stable anionic mesoporous MOF based on uranium and featuring tbo-type topology. The resulting tbo MOF exhibits exceptionally large open cavities (3.9 nm) exceeding those of all known anionic MOFs. By supercritical CO2 activation, a record-high Brunauer-Emmett-Teller (BET) surface area (2100 m(2) g(-1) ) for actinide-based MOFs has been obtained. Most importantly, however, this new uranium-based MOF is water-stable and able to absorb positively charged ions selectively over negatively charged ones, enabling the efficient separation of organic dyes and biomolecules.

Allosteric Modulation of Substrate Binding within a Tetracationic Molecular Receptor.

The synthesis and recognition phenomena of a tetracationic molecular receptor that possesses a nanometer-sized molecular cavity are described. The host-guest properties of the molecular receptor can be tuned and modulated allosterically, where the association of a heterotropic effector at the periphery of the molecule serves to modulate its affinity for the globular, electron-rich guest that resides within its molecular cavity. This stimuli-responsive host-guest behavior was observed in both the solution phase and the crystalline solid state, and can be reversed with high fidelity by sequestration of the effector molecule.

Catenation through a Combination of Radical Templation and Ring-Closing Metathesis.

Synthesis of an electrochemically addressable [2]catenane has been achieved following formation by templation of a [2]pseudorotaxane employing radically enhanced molecular recognition between the bisradical dication obtained on reduction of the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), and the radical cation generated on reduction of a viologen disubstituted with p-xylylene units, both carrying tetraethylene glycol chains terminated by allyl groups. This inclusion complex was subjected to olefin ring-closing metathesis, which was observed to proceed under reduced conditions, to mechanically interlock the two components. Upon oxidation, Coulombic repulsion between the positively charged and mechanically interlocked components results in the adoption of a co-conformation where the newly formed alkene resides inside the cavity of the tetracationic cyclophane. (1)H NMR spectroscopic analysis of this hexacationic [2]catenane shows a dramatic upfield shift of the resonances associated with the olefinic and allylic protons as a result of them residing inside the tetracationic component. Further analysis shows high diastereoselectivity during catenation, as only a single (Z)-isomer is formed.

Energy and Electron Transfer Dynamics within a Series of Perylene Diimide/Cyclophane Systems.

Artificial photosynthetic systems for solar energy conversion exploit both covalent and supramolecular chemistry to produce favorable arrangements of light-harvesting and redox-active chromophores in space. An understanding of the interplay between key processes for photosynthesis, namely light-harvesting, energy transfer, and photoinduced charge separation and the design of novel, self-assembling components capable of these processes are imperative for the realization of multifunctional integrated systems. We report our investigations on the potential of extended tetracationic cyclophane/perylene diimide systems as components for artificial photosynthetic applications. We show how the selection of appropriate heterocycles, as extending units, allows for tuning of the electron accumulation and photophysical properties of the extended tetracationic cyclophanes. Spectroscopic techniques confirm energy transfer between the extended tetracationic cyclophanes and perylene diimide is ultrafast and quantitative, while the heterocycle specifically influences the energy transfer related parameters and the acceptor excited state.

Ultrahigh surface area zirconium MOFs and insights into the applicability of the BET theory.

An isoreticular series of metal-organic frameworks (MOFs) with the ftw topology based on zirconium oxoclusters and tetracarboxylate linkers with a planar core (NU-1101 through NU-1104) has been synthesized employing a linker expansion approach. In this series, NU-1103 has a pore volume of 2.91 cc g(-1) and a geometrically calculated surface area of 5646 m(2) g(-1), which is the highest value reported to date for a zirconium-based MOF and among the largest that have been reported for any porous material. Successful activation of the MOFs was proven based on the agreement of pore volumes and BET areas obtained from simulated and experimental isotherms. Critical for practical applications, NU-1103 combines for the first time ultrahigh surface area and water stability, where this material retained complete structural integrity after soaking in water. Pressure range selection for the BET calculations on these materials was guided by the four so-called "consistency criteria". The experimental BET area of NU-1103 was 6550 m(2) g(-1). Insights obtained from molecular simulation suggest that, as a consequence of pore-filling contamination, the BET method overestimates the monolayer loading of NU-1103 by ∼16%.

A Hafnium-Based Metal-Organic Framework as a Nature-Inspired Tandem Reaction Catalyst.

Tandem catalytic systems, often inspired by biological systems, offer many advantages in the formation of highly functionalized small molecules. Herein, a new metal-organic framework (MOF) with porphyrinic struts and Hf6 nodes is reported. This MOF demonstrates catalytic efficacy in the tandem oxidation and functionalization of styrene utilizing molecular oxygen as a terminal oxidant. The product, a protected 1,2-aminoalcohol, is formed selectively and with high efficiency using this recyclable heterogeneous catalyst. Significantly, the unusual regioselective transformation occurs only when an Fe-decorated Hf6 node and the Fe-porphyrin strut work in concert. This report is an example of concurrent orthogonal tandem catalysis.

Functionalized defects through solvent-assisted linker exchange: synthesis, characterization, and partial postsynthesis elaboration of a metal-organic framework containing free carboxylic acid moieties.

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.

Modulating the binding of polycyclic aromatic hydrocarbons inside a hexacationic cage by anion-π interactions.

We report the template-directed synthesis of BlueCage(6+), a macrobicyclic cyclophane composed of six pyridinium rings fused with two central triazines and bridged by three paraxylylene units. These moieties endow the cage with a remarkably electron-poor cavity, which makes it a powerful receptor for polycyclic aromatic hydrocarbons (PAHs). Upon forming a 1:1 complex with pyrene in acetonitrile, however, BlueCage⋅6 PF6 exhibits a lower association constant Ka than its progenitor ExCage⋅6 PF6. A close inspection reveals that the six PF6(-) counterions of BlueCage(6+) occupy the cavity in a fleeting manner as a consequence of anion-π interactions and, as a result, compete with the PAH guests. This conclusion is supported by a one order of magnitude increase in the Ka value for pyrene in BlueCage(6+) when the PF6(-) counterions are replaced by much bulkier anions. The presence of anion-π interactions is supported by X-ray crystallography, and confirms the presence of a PF6(-) counterion inside its cavity.