Effective Dual-Functional Metal-Organic Framework (DF-MOF) as a Catalyst for the Solvent-Free Cycloaddition Reaction.

A new porous metal-organic framework, [Co (oba) (bpdh)]·(DMF) (TMU-63), containing accessible nitrogen-rich diazahexadiene groups was successfully prepared with the solvothermal assembly of 5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh), 4,4'-oxybis(benzoic) acid (oba), and Co(II) ions. The combination of Lewis basic functional groups and porosity leads to high performance in CO2 adsorption and conversion in the cycloaddition reaction of epoxides under solvent-free conditions. To further enhance the catalytic efficiency of TMU-63, we introduced a highly acidic malonamide ligand into the structure via solvent-assisted ligand exchange (SALE) as a postsynthesis method. Incorporating different percentages of N1,N3-di(pyridine-4-yl) malonamide linker (4-dpm) into TMU-63 created a new porous structure. Powder X-ray diffraction (PXRD) and NMR spectroscopy confirmed that 4-bpdh was successfully replaced with 4-dpm in the daughter MOF, TMU-63S. The catalytic activity of both MOFs was confirmed by significant amounts of CO2 cycloaddition of epoxides under solvent-free conditions. The catalytic cycloaddition activities were found to be well-correlated with the Lewis base/Brønsted acid distributions of the materials examined in the TMU-63S series, showing that the concurrent presence of both acid and base sites was desirable for high catalytic activity. Furthermore, the heterogeneous catalysts could easily be separated out from the reaction mixtures and reused four times without loss of catalytic activity and with no structural deterioration.

Coordinatively unsaturated metal sites (open metal sites) in metal-organic frameworks: design and applications.

Metal-organic frameworks (MOFs) can contain open metal sites (OMS) or coordinatively unsaturated sites (CUS) or open coordination sites (OCS) when vacant Lewis acid sites on the metal ions or cluster nodes have been generated. This review combines for the first time all aspects of OMS in MOFs, starting from different preparation strategies over theoretical studies on the effects of OMS with host-guest interactions up to distinct OMS-MOF applications. In the experimental part the focus of this review is on MOFs with proven OMS formation which are not only invoked but are clearly verified by analytical methods.

Size-Selective Urea-Containing Metal-Organic Frameworks as Receptors for Anions.

Anion recognition by neutral hosts that function in aqueous solution is an emerging area of interest in supramolecular chemistry. The design of neutral architectures for anion recognition still remains a challenge. Among neutral anion receptor systems, urea and its derivatives are considered as "privileged groups" in supramolecular anion recognition, since they have two proximate polarized N-H bonds exploitable for anion recognition. Despite promising advancements in urea-based structures, the strong hydrogen bond drives detrimental self-association. Therefore, immobilizing urea fragments onto the rigid structures of a metal-organic framework (MOF) would prevent this self-association and promote hydrogen-bond-accepting substrate recognition. With this aim, we have synthesized two new urea-containing metal-organic frameworks, namely [Zn(bpdc)(L2)]n·nDMF (TMU-67) and [Zn2(bdc)2(L2)2]n·2nDMF (TMU-68) (bpdc = biphenyl-4,4'-dicarboxylate; bdc = terephthalate; L2 = 1,3-bis(pyridin-4-yl)urea), and we have assessed their recognition ability toward different anions in water. The two MOFs show good water stability and anion affinity, with a particular selectivity toward dihydrogen arsenate for TMU-67 and toward fluoride for TMU-68. Crystal structure characterizations reveal 3-fold and 2-fold interpenetrated 3D networks for TMU-67 and TMU-68, respectively, where all single interpenetrated networks are hydrogen bonded to each other in both cases. Despite the absence of self-quenching, the N-H urea bonds are tightly hydrogen bonded to the oxygen atoms of the dicarboxylate ligands and cannot be directly involved in the recognition process. The good performance in anion sensing and selectivity of the two MOFs can be ascribed to the network interpenetration that, shaping the void, creates monodimensional channels, decorated by exposed oxygen atom sites selective for arsenate sensing in TMU-67 and isolated cavities, covered by phenyl groups selective for fluoride recognition in TMU-68.

Urea Metal-Organic Frameworks for Nitro-Substituted Compounds Sensing.

Urea groups are known to form strong hydrogen bonds with molecules containing atom(s) that can act as hydrogen bond acceptor(s). Thus, urea is a particularly interesting building block for designing receptors for neutral or charged guests. In the quest for new sensors with enhanced performance for the detection of nitro-substituted compounds, two pillared metal-organic frameworks containing urea functional groups were synthesized and structurally characterized. The sensing properties of these frameworks toward nitro-analytes were investigated and compared to each other. The study clearly reveals the importance of urea groups orientation inside the pore cavity of MOFs, as well as the supramolecular interactions between the interpenetrated networks. This work is interesting as it represents the first example of urea-functionalized MOFs for nitro-analytes recognition.

Ultrasound Irradiation Assisted Synthesis of Luminescent Nano Amide-Functionalized Metal-Organic Frameworks; Application Toward Phenol Derivatives Sensing.

Two nano amide-functionalized metal-organic frameworks (MOFs) with molecular formula [Co(oba) (bpta)]·(DMF)2 TMU-50 and [Co2(oba)2 (bpfn)]·(DMF)2.5 TMU-51 obtained under ultrasonic method without any surfactants. The only difference between the two selected amide functionalized pillar ligands, N,N'-bis(4-pyridinyl)-terephthalamide (bpta), and N,N'-bis-(4-pyridylformamide)-1,5-naphthalenediamine (bpfn), is related to the naphthyl group, which led to the different luminescence properties of the nano frameworks. In this study, the special ability of the luminescent nano MOFs were investigated to sensitize nitroaromatic compounds. Due to its unique and porous framework, Nano TMU-50 shows a good sensitivity towards nitro phenol by strong fluorescence emission with a detection limit of 2 × 10-3 mM-1. Both nano MOF structures were characterized via many analyses such as powder X-ray diffraction, Field Emission Scanning Electron Microscopy (FE-SEM), elemental analysis, and FTIR spectroscopy. Moreover, the effect of a number of important parameters including initial reagent concentrations, power of ultrasound, time on morphology, and size of nano structures were examined. According to the fluorescence titration results, the activated nano-TMU-50 detected NP selectively with a quick response.

Reuse of Predesigned Dual-Functional Metal Organic Frameworks (DF-MOFs) after Heavy Metal Removal.

Designing porous and functionalized adsorbents and achieving high efficiency in heavy metals removal from wastewater is in the spotlight of environmental science. On the other hand, upon removal, adsorbents are still highly hazardous requiring that great care be taken in its packaging, transporting and storing. A fundamental route in the synthesis of functional extended structures is the ability to combine different chemical entities in a controlled way in order to achieve high performance. Herein, we report the systematic design of dual-functionalized metal organic framework (TMU-81) by incorporating sulfonyl and amide groups for the removal of Cd(II), Cu(II) and Cr(II) ions from simulated aqueous solutions. TMU-81 showed significant enhancement in heavy metals uptake suggesting that the strong host - guest interactions between cations and the donor sites play a major role in adsorption process. The maximum adsorption capacity for Cd2+ was 526 mg/g which is among the highest values reported for similar MOFs and other porous materials. The good performance in uptake and selectivity of TMU-81 can be attributed to the network structure that shaping the void, create mono-dimensional channels, decorated by exposed oxygen atom sites selective for Cadmium ion. Environmental "compatibility" of a treated MOFs was studied in order to evaluate its possible recycling as a new template for different applications by using pyrolysis method. Engineering of the pore surface provides a potential for MOF with a hybrid interface to act as a versatile tool for the design of multifunctional nanoparticles to meet specific application requirements.

Rational morphology control of nano-scale amide decorated metal-organic frameworks by ultrasonic method: Capability to selective and sensitive detection of nitro explosives.

One of the key challenges in rational design and synthesis of metal-organic frameworks (MOFs) is defined control over size and morphology for using these materials in many more advanced applications. Combining ultrasonic method and capping groups makes it possible to control the size and change the morphology of metal organic frameworks without changing material compositions. Nano TMU-46, 47 and 48 with copper metal center and amide functionalized pillar were synthesized by using ultrasonic irritation and characterized by FE-SEM, powder X-ray diffraction, elemental analysis, and FTIR spectroscopy. Sensing properties of these nano scale materials and the correlation between the nano structure and nitroaromatic compounds detection were studied. Nano TMU-46 due to its special and porous structure and available functional group show strong luminescence emission, which is selectively sensitive to Trinitrophenol (TNP) with a detection limit of 10-3 M. Furthermore, multiple morphological transition in the structure of these crystals were observed with using different modulators. This morphology transition, in fact, successfully led to significant change in sensing properties of this structure and decreased the detection limit to 10-5 M.

Development of Porous Cobalt-/Copper-Doped Carbon Nanohybrids Derived from Functionalized MOFs as Efficient Catalysts for the Ullmann Cross-Coupling Reaction: Insights into the Active Centers.

Newly emerging poly-functional metal-organic frameworks (MOFs) have been proved to be a promising alternative method for the hard/soft template to generate different carbon-based heterostructures. Herein, we have synthesized a sulfonyl-amide-based MOF (TMU-81) with an exceptionally high concentration of functional groups, which can interact strongly with metal ions and utilized it as a double-template platform to fabricate versatile catalysts by remaining structural regularity. The preloaded copper ions resided in pores of TMU-81 not only play a significant role in pore-forming by in situ renovating into Cu nanoparticles via the pyrolysis process but also trigger the morphological transformations of the resultant metal/carbon hybrids. The morphology of the TMU-81 was tuned from truncated octahedron to cubic in cobalt-/copper-doped carbon nanohybrids (MC-81), and also the Brunauer-Emmett-Teller surface area increased significantly up to 1450 cm2/g. Benchmarks have been established for the performance of TMU-81, pyrolyzed TMU-81 (P-TMU-81), and MC-81s, as efficient and robust catalysts for the C-N cross-coupling reaction with aryl-halides and amines. The obtained MC-81 showed superior performance compared with pristine TMU-81 and pyrolyzed P-TMU-81. The catalysis performance is found to be closely dependent on the amount of preloaded Cu2+ ions in the MOFs. After 5 cycles, the catalysts were reusable without any significant loss of activity. Benefiting from the structural and compositional advantages, the present approach offers an intelligent way to synthesis and design of structurally complex MOF hybrid and derived functionalized systems.

The targeted design of dual-functional metal-organic frameworks (DF-MOFs) as highly efficient adsorbents for Hg2+ ions: synthesis for purpose.

Designing adsorbents with accessible chelating sites and achieving high contaminant purification efficiency are still important to overcome environmental remediation challenges. As one of the significant global concerns, the presence of heavy metal ions in the environment has attracted increasing attention due to their toxicity, carcinogenicity, and bioaccumulation in the food chain. Herein, we performed a targeted design of a new dual-functionalized metal-organic framework (DF-MOF) by incorporating different percentages of the N1,N3-di(pyridine-4-yl) malonamide ligand (S) into urea-containing MOF (TMU-32); the produced material was labeled as TMU-32S (with 33%, 65%, and 100% incorporation percentages). Designing DF-MOF is our "design-for-purpose" approach for the decoration of MOF walls by suitable functional groups, resulting in high removal capacity of heavy metal ions. Among the TMU-32S series having different concentrations of the S ligand, TMU-32S-65% demonstrated exceptional Hg2+ ion selectively. To the best of our knowledge, this is the first report of mixed urea-malonamide-based MOF, which provides a proper coordination site to strongly coordinate with Hg2+ ions, along with 1428 mg g-1 maximum adsorption capacity. Generally, we attributed the impressive implementation of TMU-32S-65% to the synergistic effects of both hydrophilic chelating urea and the malonamide functional group. Hence, the results reported in this work indicate the exceptional potential of DF-MOFs for the high accomplishment of environmental remediation.

Solvent-assisted ligand exchange (SALE) for the enhancement of epoxide ring-opening reaction catalysis based on three amide-functionalized metal-organic frameworks.

In recent years, functionalized pillar ligands have gained significant interests due to their important role in MOF structure and performance. The synthesis of MOF compounds with a particular functionalized ligand is not always successful, and sometimes, synthesis cannot be achieved easily or directly, even by employing several methods. However, this limitation can be overcome by applying a post-synthesis step that swaps the functional groups without changing the backbone of the pillar ligand. Solvent-assisted ligand exchange (SALE) is a post-synthesis method that has been used for confronting this challenge by replacing a functional group with an alternative. Through this investigation, we tried to improve the properties of MOF compounds and increase their catalytic efficiency by importing new functional groups into their structures. The N1,N3-di (pyridine-4-yl) malonamide linker (S) is a pillar ligand, which does not easily enter into the structure during the synthesis of MOF compounds. Therefore, to solve this issue, amide-functionalized, benzene-core ligand derivatives were designed as linkers to manufacture the new 3D structures [Co(oba)(bpta)]·(DMF)2 TMU-50 and [Co2(oba)2(bpfn)]·(DMF)2.5 TMU-51 and the novel 2D structure [Co(oba)(bpfb)]·(DMF)2 TMU-49. These structures were achieved by layering the compounds via hydrothermal reaction. Moreover, the ability of these structures to act as catalysts was evaluated using the methanolysis reaction of epoxides. To increase the MOF catalytic efficiency, we designed the N1,N3-di (pyridine-4-yl) malonamide linker (S) as a malonamide pillar ligand, which contains an acidic hydrogen that is suitable for catalyzing an epoxide ring-opening reaction and therefore enhancing the catalytic activity. As the synthesis of the MOF structure with this linker was not successful, we designed three new structures by incorporating different percentages of S linkers by exchanging the acylamide functional group with malonamide via the SALE pathway. The acylamide functional group was successfully replaced and produced daughter MOFs TMU-49S, TMU-50S and TMU-51S. PXRD and NMR spectroscopy confirmed that the S linker was incorporated into the acylamide-MOF structure. The obtained materials TMU-49S, TMU-50S and TMU-51S are isostructural with their parent frameworks. The S spacer significantly improved the catalytic properties of the MOF compounds in the ring-opening reaction of epoxides, with TMU-50S showing a 98% catalytic efficiency after incorporating the S linker. The catalysts could be recycled without any significant loss in the catalytic efficiency.

Ultrasonic assisted synthesis of two urea functionalized metal organic frameworks for phenol sensing: A comparative study.

Two pillared metal-organic frameworks containing urea functional groups were synthesized by a sonochemical method and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analysis. The time of sonication and concentration of starting materials have been optimized to synthesize nanoparticles of TMU-31 and TMU-32. These two frameworks are interesting candidates for a comparative fluorescence study. Thus, their potential abilities for phenol sensing were investigated. This investigation revealed the prominent roles of hydrogen bond donating urea groups inside the pore cavity in the ability of these structures in phenol sensing.