47 results on '"Inge, A. Ken"'
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2. Metal-Organic Frameworks: Unconventional Nanoweapons against COVID.
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Álvarez-Miguel I, Fodor B, López GG, Biglione C, Grape ES, Inge AK, Hidalgo T, and Horcajada P
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- Humans, Chlorocebus aethiops, Vero Cells, Cell Survival drug effects, Metal-Organic Frameworks chemistry, Metal-Organic Frameworks pharmacology, SARS-CoV-2 drug effects, Antiviral Agents chemistry, Antiviral Agents pharmacology, Antiviral Agents therapeutic use, COVID-19 Drug Treatment, COVID-19 virology
- Abstract
The SARS-CoV-2 (COVID-19) pandemic outbreak led to enormous social and economic repercussions worldwide, felt even to this date, making the design of new therapies to combat fast-spreading viruses an imperative task. In the face of this, diverse cutting-edge nanotechnologies have risen as promising tools to treat infectious diseases such as COVID-19, as well as challenging illnesses such as cancer and diabetes. Aside from these applications, nanoscale metal-organic frameworks (nanoMOFs) have attracted much attention as novel efficient drug delivery systems for diverse pathologies. However, their potential as anti-COVID-19 therapeutic agents has not been investigated. Herein, we propose a pioneering anti-COVID MOF approach by studying their potential as safe and intrinsically antiviral agents through screening various nanoMOF. The iron(III)-trimesate MIL-100 showed a noteworthy antiviral effect against SARS-CoV-2 at the micromolar range, ensuring a high biocompatibility profile (90% of viability) in a real infected human cellular scenario. This research effectively paves the way toward novel antiviral therapies based on nanoMOFs, not only against SARS-CoV-2 but also against other challenging infectious and/or pulmonary diseases.
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- 2024
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3. SU-101 for the removal of pharmaceutical active compounds by the combination of adsorption/photocatalytic processes.
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Chacón-García AJ, Rojas S, Grape ES, Salles F, Willhammar T, Inge AK, Pérez Y, and Horcajada P
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- Humans, Adsorption, Wastewater, Atenolol, Diclofenac, Water, Pharmaceutical Preparations, Water Pollutants, Chemical analysis, Metal-Organic Frameworks chemistry
- Abstract
Pharmaceutical active compounds (PhACs) are some of the most recalcitrant water pollutants causing undesired environmental and human effects. In absence of adapted decontamination technologies, there is an urgent need to develop efficient and sustainable alternatives for water remediation. Metal-organic frameworks (MOFs) have recently emerged as promising candidates for adsorbing contaminants as well as providing photoactive sites, as they possess exceptional porosity and chemical versatility. To date, the reported studies using MOFs in water remediation have been mainly focused on the removal of a single type of PhACs and rarely on the combined elimination of PhACs mixtures. Herein, the eco-friendly bismuth-based MOF, SU-101, has been originally proposed as an efficient adsorbent-photocatalyst for the elimination of a mixture of three challenging persistent PhACs, frequently detected in wastewater and surface water in ng L
-1 to mg·L-1 concentrations: the antibiotic sulfamethazine (SMT), the anti-inflammatory diclofenac (DCF), and the antihypertensive atenolol (At). Adsorption experiments of the mixture revealed that SU-101 exhibited a great adsorption capacity towards At, resulting in an almost complete removal (94.1 ± 0.8% for combined adsorption) in only 5 h. Also, SU-101 demonstrated a remarkable photocatalytic activity under visible light to simultaneously degrade DCF and SMT (99.6 ± 0.4% and 89.2 ± 1.4%, respectively). In addition, MOF-contaminant interactions, the photocatalytic mechanism and degradation pathways were investigated, also assessing the toxicity of the resulting degradation products. Even further, recycling and regeneration studies were performed, demonstrating its efficient reuse for 4 consecutive cycles without further treatment, and its subsequent successful regeneration by simply washing the material with a NaCl solution., (© 2024. The Author(s).)- Published
- 2024
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4. Structure-reactivity analysis of novel hypervalent iodine reagents in S -vinylation of thiols.
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Doobary S, Di Tommaso EM, Postole A, Inge AK, and Olofsson B
- Abstract
The transition-metal free S -vinylation of thiophenols by vinylbenziodoxolones (VBX) constituted an important step forward in hypervalent iodine-mediated vinylations, highlighting the difference to vinyliodonium salts and that the reaction outcome was influenced by the substitution pattern of the benziodoxolone core. In this study, we report several new classes of hypervalent iodine vinylation reagents; vinylbenziodazolones, vinylbenziodoxolonimine and vinyliodoxathiole dioxides. Their synthesis, structural and electronic properties are described and correlated to the S -vinylation outcome, shedding light on some interesting facets of these reagents., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Doobary, Di Tommaso, Postole, Inge and Olofsson.)
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- 2024
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5. Discovery and In Situ Crystallization Studies of Cerium-Based Metal-Organic Frameworks with V-Shaped Linker Molecules.
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Gosch J, Guiotto V, Steinke F, Svensson Grape E, Atzori C, Mertin K, Otto T, Ruser N, Meier C, Morelli Venturi D, Inge AK, Lomachenko KA, Crocellà V, and Stock N
- Abstract
We report the discovery and characterization of two porous Ce(III)-based metal-organic frameworks (MOFs) with the V-shaped linker molecules 4,4'-sulfonyldibenzoate (SDB
2- ) and 4,4'-(hexafluoroisopropylidene)bis(benzoate) (hfipbb2- ). The compounds of framework composition [Ce2 (H2 O)(SDB)3 ] ( 1 ) and [Ce2 (hfipbb)3 ] ( 2 ) were obtained by using a synthetic approach in acetonitrile that we recently established. Structure determination of 1 was accomplished from 3D electron diffraction (3D ED) data, while 2 could be refined against powder X-ray diffraction (PXRD) data using the crystal structure of an isostructural La-MOF as the starting model. Their framework structures consist of chain-like inorganic building units (IBUs) or hybrid-BUs that are interconnected by the V-shaped linker molecules to form framework structures with channel-type pores. The composition of both compounds was confirmed by PXRD, elemental analysis, as well as NMR and IR spectroscopy. Interestingly, despite the use of (NH4 )2 [CeIV (NO3 )6 ] in the synthesis, cerium ions in both MOFs occur exclusively in the + III oxidation state as determined by X-ray absorption near edge structure (XANES) and X-ray photoelectron spectroscopy (XPS). Thermal analyses reveal remarkably high thermal stabilities of ≥400 °C for the MOFs. Initial N2 sorption measurements revealed the peculiar sorption behavior of 2 which prompted a deeper investigation by Ar and CO2 sorption experiments. The combination with nonlocal density functional theory (NL-DFT) calculations adds to the understanding of the nature of the different pore diameters in 2 . An extensive quasi-simultaneous in situ XANES/XRD investigation was carried out to unveil the formation of Ce-MOFs during the solvothermal syntheses in acetonitrile. The crystallization of the two Ce(III)-MOFs presented herein as well as two previously reported Ce(IV)-MOFs, all obtained by a similar synthetic approach, were studied. While the XRD patterns show time-dependent MOF crystallization, the XANES data reveal the presence of Ce(III) intermediates and their subsequent conversion to the MOFs. The addition of acetic acid in combination with the V-shaped linker molecule was identified as the crucial factor for the formation of the crystalline Ce(III/IV)-MOFs.- Published
- 2023
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6. Electrochromism in Isoreticular Metal-Organic Framework Thin Films with Record High Coloration Efficiency.
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Kumar A, Li J, Inge AK, and Ott S
- Abstract
The power of isoreticular chemistry has been widely exploited to engineer metal-organic frameworks (MOFs) with fascinating molecular sieving and storage properties but is underexplored for designing MOFs with tunable optoelectronic properties. Herein, three dipyrazole-terminated XDIs (X = PM (pyromellitic), N (naphthalene), or P (perylene); DI = diimide) with different lengths and electronic properties are prepared and employed as linkers for the construction of an isoreticular series of Zn-XDI MOFs with distinct electrochromism. The MOFs are grown on fluorine-doped tin oxide (FTO) as high-quality crystalline thin films and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Due to the constituting electronically isolated XDI linkers, each member of the isoreticular thin film series exhibits two reversible one-electron redox events, each at a distinct electrochemical potential. The orientation of the MOFs as thin films as well as their isoreticular nature results in identical cation-coupled electron hopping transport rates in all three materials, as demonstrated by comparable apparent electron diffusion coefficients, D
e app state, each MOF undergoes characteristic changes in its optical properties as a function of linker length and redox state of the linker. Operando spectroelectrochemistry measurements reveal that Zn-PDI@FTO (PDI = perylene diimide) thin films exhibit a record high coloration efficiency of 941 cm•- or [XDI]2- state, each MOF undergoes characteristic changes in its optical properties as a function of linker length and redox state of the linker. Operando spectroelectrochemistry measurements reveal that Zn-PDI@FTO (PDI = perylene diimide) thin films exhibit a record high coloration efficiency of 941 cm2 C-1 at 746 nm, which is attributed to the maximized Faradaic transformations at each electronically isolated PDI unit. The electrochromic response of the thin film is retained to more than 99% over 100 reduction-oxidation cycles, demonstrating the applicability of the presented materials.- Published
- 2023
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7. Sugar-Assisted Kinetic Resolutions in Metal/Chiral Amine Co-Catalyzed α-Allylations and [4+2] Cycloadditions: Highly Enantioselective Synthesis of Sugar and Chromane Derivatives.
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Zhang K, Carmo C, Deiana L, Grape ES, Inge AK, and Córdova A
- Abstract
Functionalized triose-, furanose and chromane-derivatives were synthesized by the titled reactions. The sugar-assisted kinetic resolution/C-C bond-forming cascade processes generate a functionalized sugar derivative with a quaternary stereocenter in a highly enantioselective fashion (up to >99 % ee) by using a simple combination of metal and chiral amine co-catalysts. Notably, the interplay between the chiral sugar substrate and the chiral amino acid derivative allowed for the construction of a functionalized sugar product with high enantioselectivity (up to 99 %) also when using a combination of racemic amine catalyst (0 % ee) and metal catalyst., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
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- 2023
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8. Porous Salts Containing Cationic Al 24 -Hydroxide-Acetate Clusters from Scalable, Green and Aqueous Synthesis Routes.
- Author
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Achenbach B, Grape ES, Wahiduzzaman M, Pappler SK, Meinhart M, Siegel R, Maurin G, Senker J, Inge AK, and Stock N
- Abstract
The solution chemistry of aluminum is highly complex and various polyoxocations are known. Here we report on the facile synthesis of a cationic Al
24 cluster that forms porous salts of composition [Al24 (OH)56 (CH3 COO)12 ]X4 , denoted CAU-55-X, with X=Cl- , Br- , I- , HSO4 - . Three-dimensional electron diffraction was employed to determine the crystal structures. Various robust and mild synthesis routes for the chloride salt [Al24 (OH)56 (CH3 COO)12 ]Cl4 in water were established resulting in high yields (>95 %, 215 g per batch) within minutes. Specific surface areas and H2 O capacities with maximum values of up to 930 m2 g-1 and 430 mg g-1 are observed. The particle size of CAU-55-X can be tuned between 140 nm and 1250 nm, permitting its synthesis as stable dispersions or as highly crystalline powders. The positive surface charge of the particles, allow fast and effective adsorption of anionic dye molecules and adsorption of poly- and perfluoroalkyl substances (PFAS)., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)- Published
- 2023
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9. Encapsulation of dopamine within SU-101: insights by computational chemistry.
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Medel E, Obeso JL, Serrano-Fuentes C, Garza J, Ibarra IA, Leyva C, Inge AK, Martínez A, and Vargas R
- Abstract
Encapsulating and protecting dopamine from oxidation is a difficult challenge. We propose to use SU-101 BioMOF as a dopamine host, where we study different adsorption scenarios by a robust computational approach. Our results show that dopamine encapsulation is feasible with the formation of non-covalent interactions within the SU-101 pores. These computational results have been corroborated experimentally.
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- 2023
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10. Stereospecific Photoredox-Catalyzed Vinylations to Functionalized Alkenes and C-Glycosides.
- Author
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Bhaskar Pal K, Di Tommaso EM, Inge AK, and Olofsson B
- Abstract
We report an efficient radical-mediated C-C coupling through photoredox-catalyzed reactions of 4-alkyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition-metal-free and mild photocatalytic method has excellent functional group tolerance and affords vinylated products in good yields, with complete retention of the alkene configuration. The utility of the methodology is demonstrated by the diastereoselective synthesis of C-vinyl glycosides. Preliminary mechanistic studies suggest that the C-C bond formation is stereospecific and proceeds through a concerted radical coupling transition state., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
- Published
- 2023
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11. Synthesis, Crystal Structure, and Photocatalytic Properties of Two Isoreticular Ce(IV)-MOFs with an Infinite Rod-Shaped Inorganic Building Unit.
- Author
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Gosch J, Morelli Venturi D, Svensson Grape E, Atzori C, Donà L, Steinke F, Otto T, Tjardts T, Civalleri B, Lomachenko KA, Inge AK, Costantino F, and Stock N
- Abstract
The use of the V-shaped linker molecules 4,4'-oxydibenzoic acid (H
2 ODB) and 4,4'-carbonyldibenzoic acid (H2 CDB) led to the discovery of two isoreticular Ce(IV)-based metal-organic frameworks (MOFs) of composition [CeO(H2 O)(L)], L = ODB2- , CDB2- , denoted CAU-58 (CAU = Christian-Albrechts-University). The recently developed Ce-MOF synthesis approach in acetonitrile as the solvent proved effective in accessing Ce(IV)-MOF structures with infinite rod-shaped inorganic building units (IBUs) and circumventing the formation of the predominantly observed hexanuclear [Ce6 O8 ] cluster. For the structure determination of the isoreticular MOFs, three-dimensional electron diffraction (3D ED) and powder X-ray diffraction (PXRD) data were used in combination with density functional theory (DFT) calculations. [CeO(H2 O)(CDB)] shows reversible H2 O adsorption by stirring in water and thermal treatment at 190 °C, which leads to a unit cell volume change of 11%. The MOFs feature high thermal stabilities ( T > 290 °C), which exceed those of most Ce(IV)-MOFs and can be attributed to the infinite rod-shaped IBU. Surface and bulk oxidation states of the cerium ions were analyzed via X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES). While Ce(III) ions are observed by the highly surface-sensitive XPS method, the bulk material contains predominantly Ce(IV) ions according to XANES. Application of the MOFs as catalysts for the catalytic degradation of methyl orange in aqueous solutions was also studied. While degradation activity for both MOFs was observed, only CAU-58-ODB revealed enhanced photocatalytic activity under ultraviolet (UV) light. The photocatalytic mechanism likely involves a ligand-to-metal charge transfer (LMCT) from the linkers to the Ce(IV) centers. Analyses by XANES and inductively coupled plasma-optical emission spectroscopy (ICP-OES) demonstrate that leaching of Cerium ions as well as partial reduction of Ce(IV) to Ce(III) takes place during catalysis. At the same time, PXRD data confirm the structural stability of the remaining MOF catalysts.- Published
- 2023
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12. Bismuth gallate coordination networks inspired by an active pharmaceutical ingredient.
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Svensson Grape E, Rooth V, Smolders S, Thiriez A, Takki S, De Vos D, Willhammar T, and Inge AK
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- Bismuth chemistry, Lewis Acids, Methanol, Pharmaceutical Preparations, Polymers chemistry, Solvents, Water, Metal-Organic Frameworks, Phenylethyl Alcohol
- Abstract
The effect of solvent has been investigated for the synthesis of bismuth gallate compounds, of which the water-based bismuth subgallate has been used as an active pharmaceutical ingredient (API) for over a century. Using methanol as a solvent, two new bismuth gallates were acquired: first a flexible 3-periodic metal-organic framework (MOF) forms, which transforms upon extended synthesis times into a layered 2-periodic coordination polymer of the same bismuth-to-gallate ratio. The structures were determined by three-dimensional electron diffraction. Synthesis in ethanol resulted in the formation of the MOF phase, but not the layered phase. The layered material of the methanol-based synthesis was used as a Lewis acid catalyst due to its higher stability, showing a comparatively quick and regiospecific conversion of styrene oxide to 2-methoxy-2-phenylethanol, indicating the presence of open metal sites in the material. The acquisition of bismuth gallate structures of varying periodicity highlights the prospect of acquiring novel MOFs and coordination polymers from the same components of APIs.
- Published
- 2022
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13. Triple helix and rod structures of the antiseptic drug bibrocathol revealed by electron crystallography.
- Author
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Svensson Grape E, Willhammar T, and Inge AK
- Subjects
- Catechols, Crystallography methods, Crystallography, X-Ray, Ointments, Anti-Infective Agents, Local pharmacology, Electrons
- Abstract
Bibrocathol is an active pharmaceutical ingredient that has been used to treat eyelid diseases for over a century, yet its structure has remained unknown. 3D electron diffraction on crystals from a commercial ointment revealed two structures. These results highlight the technique's potential in structure elucidation from microcrystalline mixtures.
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- 2022
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14. Synthesis of α,γ-Chiral Trifluoromethylated Amines through the Stereospecific Isomerization of α-Chiral Allylic Amines.
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García-Vázquez V, Martínez-Pardo P, Postole A, Inge AK, and Martín-Matute B
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- Catalysis, Isomerism, Stereoisomerism, Amines chemistry, Imines chemistry
- Abstract
Chiral γ-branched aliphatic amines are present in a large number of pharmaceuticals and natural products. However, enantioselective methods to access these compounds are scarce and mainly rely on the use of designed chiral transition-metal complexes. Herein, we combined an organocatalytic method for the stereospecific isomerization of chiral allylic amines with a diastereoselective reduction of the chiral imine/enamine intermediates, leading to γ-trifluoromethylated aliphatic amines with two noncontiguous stereogenic centers, in excellent yields and high diastereo- and enantioselectivities. This approach has been used with primary amine substrates. This approach also provides a new synthetic pathway to chiral trifluoromethylated scaffolds, of importance in medicinal chemistry. Additionally, a gram-scale reaction demonstrates the applicability of this synthetic procedure.
- Published
- 2022
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15. Chiral Lanthanum Metal-Organic Framework with Gated CO 2 Sorption and Concerted Framework Flexibility.
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Amombo Noa FM, Grape ES, Åhlén M, Reinholdsson WE, Göb CR, Coudert FX, Cheung O, Inge AK, and Öhrström L
- Abstract
A metal-organic framework (MOF) CTH-17 based on lanthanum(III) and the conformationally chiral linker 1,2,3,4,5,6-hexakis(4-carboxyphenyl)benzene, cpb
6- : [La2 (cpb)]·1.5dmf was prepared by the solvothermal method in dimethylformamide (dmf) and characterized by variable-temperature X-ray powder diffraction (VTPXRD), variable-temperature X-ray single-crystal diffraction (SCXRD), and thermogravimetric analysis (TGA). CTH-17 is a rod-MOF with new topology och . It has high-temperature stability with Sohncke space groups P 61 22/ P 65 22 at 90 K and P 622 at 300 and 500 K, all phases characterized with SCXRD and at 293 K also with three-dimensional (3D) electron diffraction. VTPXRD indicates a third phase appearing after 620 K and stable up to 770 K. Gas sorption isotherms with N2 indicate a modest surface area of 231 m2 g-1 for CTH-17 , roughly in agreement with the crystal structure. Carbon dioxide sorption reveals a gate-opening effect of CTH-17 where the structure opens up when the loading of CO2 reaches approximately ∼0.45 mmol g-1 or 1 molecule per unit cell. Based on the SCXRD data, this is interpreted as flexibility based on the concerted movements of the propeller-like hexatopic cpb linkers, the movement intramolecularly transmitted by the π-π stacking of the cpb linkers and helped by the fluidity of the LaO6 coordination sphere. This was corroborated by density functional theory (DFT) calculations yielding the chiral phase ( P 622) as the energy minimum and a completely racemic phase ( P 6/ mmm ), with symmetric cpb linkers representing a saddle point in a racemization process.- Published
- 2022
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16. Structure of the active pharmaceutical ingredient bismuth subsalicylate.
- Author
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Svensson Grape E, Rooth V, Nero M, Willhammar T, and Inge AK
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- Bismuth, Humans, Pharmaceutical Preparations, Salicylates, Helicobacter Infections drug therapy, Organometallic Compounds
- Abstract
Structure determination of pharmaceutical compounds is invaluable for drug development but remains challenging for those that form as small crystals with defects. Bismuth subsalicylate, among the most commercially significant bismuth compounds, is an active ingredient in over-the-counter medications such as Pepto-Bismol, used to treat dyspepsia and H. pylori infections. Despite its century-long history, the structure of bismuth subsalicylate is still under debate. Here we show that advanced electron microscopy techniques, namely three-dimensional electron diffraction and scanning transmission electron microscopy, can give insight into the structure of active pharmaceutical ingredients that are difficult to characterize using conventional methods due to their small size or intricate structural features. Hierarchical clustering analysis of three-dimensional electron diffraction data from ordered crystals of bismuth subsalicylate revealed a layered structure. A detailed investigation using high-resolution scanning transmission electron microscopy showed variations in the stacking of layers, the presence of which has likely hindered structure solution by other means. Together, these modern electron crystallography techniques provide a toolbox for structure determination of active pharmaceutical ingredients and drug discovery, demonstrated by this study of bismuth subsalicylate., (© 2022. The Author(s).)
- Published
- 2022
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17. Microscopic Insights into Cation-Coupled Electron Hopping Transport in a Metal-Organic Framework.
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Castner AT, Su H, Svensson Grape E, Inge AK, Johnson BA, Ahlquist MSG, and Ott S
- Subjects
- Cations, Electron Transport, Electrons, Oxidation-Reduction, Metal-Organic Frameworks chemistry
- Abstract
Electron transport through metal-organic frameworks by a hopping mechanism between discrete redox active sites is coupled to diffusion-migration of charge-balancing counter cations. Experimentally determined apparent diffusion coefficients, D
e for charge migration through a PIZOF-type MOF, Zr(dcphOH-NDI) that is composed of redox-active naphthalenediimide (NDI) linkers, spans over 2 orders of magnitude. More importantly, however, the microscopic mechanisms for cation-coupled electron propagation are contingent on differing factors depending on the size of the cation and its propensity to engage in ion pairs with reduced linkers, either non-specifically or in defined structural arrangements. Based on computations and in agreement with experimental results, we show that ion pairing generally has an adverse effect on cation transport, thereby slowing down charge transport. In Zr(dcphOH-NDI), however, specific cation-linker interactions can open pathways for concerted cation-coupled electron transfer processes that can outcompete limitations from reduced cation flux.app , that characterize this form of charge transport thus contain contributions from both processes. While this is well established for MOFs, microscopic descriptions of this process are largely lacking. Herein, we systematically lay out different scenarios for cation-coupled electron transfer processes that are at the heart of charge diffusion through MOFs. Through systematic variations of solvents and electrolyte cations, it is shown that the De app for charge migration through a PIZOF-type MOF, Zr(dcphOH-NDI) that is composed of redox-active naphthalenediimide (NDI) linkers, spans over 2 orders of magnitude. More importantly, however, the microscopic mechanisms for cation-coupled electron propagation are contingent on differing factors depending on the size of the cation and its propensity to engage in ion pairs with reduced linkers, either non-specifically or in defined structural arrangements. Based on computations and in agreement with experimental results, we show that ion pairing generally has an adverse effect on cation transport, thereby slowing down charge transport. In Zr(dcphOH-NDI), however, specific cation-linker interactions can open pathways for concerted cation-coupled electron transfer processes that can outcompete limitations from reduced cation flux.- Published
- 2022
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18. Sacrificial W Facilitates Self-Reconstruction with Abundant Active Sites for Water Oxidation.
- Author
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Fan K, Zou H, Ding Y, Dharanipragada NVRA, Fan L, Inge AK, Duan L, Zhang B, and Sun L
- Abstract
Water oxidation is an important reaction for multiple renewable energy conversion and storage-related devices and technologies. High-performance and stable electrocatalysts for the oxygen evolution reaction (OER) are urgently required. Bimetallic (oxy)hydroxides have been widely used in alkaline OER as electrocatalysts, but their activity is still not satisfactory due to insufficient active sites. In this research, A unique and efficient approach of sacrificial W to prepare CoFe (oxy)hydroxides with abundant active species for OER is presented. Multiple ex situ and operando/in situ characterizations have validated the self-reconstruction of the as-prepared CoFeW sulfides to CoFe (oxy)hydroxides in alkaline OER with synchronous W etching. Experiments and theoretical calculations show that the sacrificial W in this process induces metal cation vacancies, which facilitates the in situ transformation of the intermediate metal hydroxide to CoFe-OOH with more high-valence Co(III), thus creating abundant active species for OER. The Co(III)-rich environment endows the in situ formed CoFe oxyhydroxide with high catalytic activity for OER on a simple flat glassy carbon electrode, outperforming those not treated by the sacrificial W procedure. This research demonstrates the influence of etching W on the electrocatalytic performance, and provides a low-cost means to improve the active sites of the in situ self-reconstructed bimetallic oxyhydroxides for OER., (© 2022 Wiley-VCH GmbH.)
- Published
- 2022
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19. Isoreticular Chemistry of Group 13 Metal-Organic Framework Compounds Based on V-Shaped Linker Molecules: Exceptions to the Rule?
- Author
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Rabe T, Grape ES, Rohr H, Reinsch H, Wöhlbrandt S, Lieb A, Inge AK, and Stock N
- Abstract
Following the concept of isoreticular chemistry, we carried out a systematic study on Ga-containing metal-organic frameworks (MOFs) using six V-shaped linker molecules of differing sizes, geometries, and additional functional groups. The linkers included three isophthalic acid derivatives ( m -H
2 BDC-R, R = CH3 , OCH3 , NHCOCH3 ), thiophene-2,5-dicarboxylic acid (H2 TDC), and two 4,4'-sulfonyldibenzoic acid derivatives (H2 SDBA, DPSTA). The crystal structures of seven compounds were elucidated by a combination of model building, single-crystal X-ray diffraction (SCXRD), three-dimensional electron diffraction (3D ED), and Rietveld refinements against powder X-ray diffraction (PXRD) data. Four new Ga-MOFs that are isoreticular with their aluminum counterparts, i.e. Ga-CAU-10-R (Ga(OH)( m -BDC-R); R = OCH3 , NHCOCH3 ), Ga-CAU-11 (Ga(OH)(SDBA)), and Ga-CAU-11-COOH (Ga(OH)(H2 DPSTC)), were obtained. For the first time large single crystals of a MOF crystallizing in the CAU-10 structure type could be isolated, i.e. Ga-CAU-10-OCH3 , which permitted a detailed structural characterization. In addition, the use of 5-methylisophthalic acid and thiophene-2,5-dicarboxylic acid resulted in two new Ga-MOFs denoted Ga-CAU-49 and Ga-CAU-51, respectively, which are not isostructural with any known Al-MOF. The crystal structure of Ga-CAU-49 ([Ga4 ( m -HBDC-CH3 )2 ( m -BDC-CH3 )3 (OH)4 (H2 O)]) contains an unprecedented rod-shaped inorganic building unit (IBU) of the formula∞ 1 {Ga16 (OH)18 O60 }, composed of corner-sharing GaO5 and GaO6 polyhedra. In Ga-CAU-51 ([Ga(OH)(C5 H2 O2 S)]) chains of alternating cis and trans polyhedra form the IBU. A detailed characterization of the title compounds was carried out, including nitrogen gas and water vapor sorption measurements. Ga-CAU-11 was the only compound exhibiting porosity toward nitrogen with a type I isotherm, a specific surface area of6 polyhedra form the IBU. A detailed characterization of the title compounds was carried out, including nitrogen gas and water vapor sorption measurements. Ga-CAU-11 was the only compound exhibiting porosity toward nitrogen with a type I isotherm, a specific surface area of a /g, and a micropore volume ofS,BET = 210 m2 /g. The new MOF Ga-CAU-51 exhibits exceptional water sorption properties with a reversible S-shaped isotherm and a high uptake around Vmic = 0.09 cm3 /g. The new MOF Ga-CAU-51 exhibits exceptional water sorption properties with a reversible S-shaped isotherm and a high uptake around p / p0 = 0.38 of mads = 370 mg/g.- Published
- 2021
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20. Metal-Dependent and Selective Crystallization of CAU-10 and MIL-53 Frameworks through Linker Nitration.
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Rabe T, Svensson Grape E, Engesser TA, Inge AK, Ströh J, Kohlmeyer-Yilmaz G, Wahiduzzaman M, Maurin G, Sönnichsen FD, and Stock N
- Abstract
The reaction of the V-shaped linker molecule 5-hydroxyisophthalic acid (H
2 L0 ), with Al or Ga nitrate under almost identical reaction conditions leads to the nitration of the linker and subsequent formation of metal-organic frameworks (MOFs) with CAU-10 or MIL-53 type structure of composition [Al(OH)(L)], denoted as Al-CAU-10-L0, 2, 4, 6 or [Ga(OH)(L)], denoted as Ga-MIL-53-L2 . The Al-MOF contains the original linker L0 as well as three different nitration products (L2 , L4 and L4/6 ), whereas the Ga-MOF mainly incorporates the linker L2 . The compositions were deduced by1 H NMR spectroscopy and confirmed by Rietveld refinement. In situ and ex situ studies were carried out to follow the nitration and crystallization, as well as the composition of the MOFs. The crystal structures were refined against powder X-ray diffraction (PXRD) data. As anticipated, the use of the V-shaped linker results in the formation of the CAU-10 type structure in the Al-MOF. Unexpectedly, the Ga-MOF crystallizes in a MIL-53 type structure, which is usually observed with linear or slightly bent linker molecules. To study the structure directing effect of the in situ nitrated linker, pure 2-nitrobenzene-1,3-dicarboxylic acid (m-H2 BDC-NO2 ) was employed which exclusively led to the formation of [Ga(OH)(C8 H3 NO6 )] (Ga-MIL-53-m-BDC-NO2 ), which is isoreticular to Ga-MIL-53-L2 . Density Functional Theory (DFT) calculations confirmed the higher stability of Ga-MIL-53-L2 compared to Ga-CAU-10-L2 and grand canonical Monte Carlo simulations (GCMC) are in agreement with the observed water adsorption isotherms of Ga-MIL-53-L2 ., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)- Published
- 2021
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21. A Tunable Multivariate Metal-Organic Framework as a Platform for Designing Photocatalysts.
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Wang Y, Lv H, Grape ES, Gaggioli CA, Tayal A, Dharanipragada A, Willhammar T, Inge AK, Zou X, Liu B, and Huang Z
- Abstract
Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO
2 . Recently, metal-organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal-organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB2 OX3 bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 molH2 gcat. -1 , a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10-1 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.-5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.- Published
- 2021
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22. Molecular Functionalization of NiO Nanocatalyst for Enhanced Water Oxidation by Electronic Structure Engineering.
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Fan L, Zhang B, Qiu Z, Dharanipragada NVRA, Timmer BJJ, Zhang F, Sheng X, Liu T, Meng Q, Inge AK, Edvinsson T, and Sun L
- Abstract
Tuning the local environment of nanomaterial-based catalysts has emerged as an effective approach to optimize their oxygen evolution reaction (OER) performance, yet the controlled electronic modulation around surface active sites remains a great challenge. Herein, directed electronic modulation of NiO nanoparticles was achieved by simple surface molecular modification with small organic molecules. By adjusting the electronic properties of modifying molecules, the local electronic structure was rationally tailored and a close electronic structure-activity relationship was discovered: the increasing electron-withdrawing modification readily decreased the electron density around surface Ni sites, accelerating the reaction kinetics and improving OER activity, and vice versa. Detailed investigation by operando Raman spectroelectrochemistry revealed that the electron-withdrawing modification facilitates the charge-transfer kinetics, stimulates the catalyst reconstruction, and promotes abundant high-valent γ-NiOOH reactive species generation. The NiO-C
6 F5 catalyst, with the optimized electronic environment, exhibited superior performance towards water oxidation. This work provides a well-designed and effective approach for heterogeneous catalyst fabrication under the molecular level., (© 2020 The Authors. Published by Wiley-VCH GmbH.)- Published
- 2020
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23. A Robust and Biocompatible Bismuth Ellagate MOF Synthesized Under Green Ambient Conditions.
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Grape ES, Flores JG, Hidalgo T, Martínez-Ahumada E, Gutiérrez-Alejandre A, Hautier A, Williams DR, O'Keeffe M, Öhrström L, Willhammar T, Horcajada P, Ibarra IA, and Inge AK
- Subjects
- Biocompatible Materials chemistry, Density Functional Theory, Metal-Organic Frameworks chemistry, Molecular Structure, Biocompatible Materials chemical synthesis, Bismuth chemistry, Ellagic Acid chemistry, Metal-Organic Frameworks chemical synthesis
- Abstract
The first bioinspired microporous metal-organic framework (MOF) synthesized using ellagic acid, a common natural antioxidant and polyphenol building unit, is presented. Bi
2 O(H2 O)2 (C14 H2 O8 )· n H2 O (SU-101) was inspired by bismuth phenolate metallodrugs, and could be synthesized entirely from nonhazardous or edible reagents under ambient aqueous conditions, enabling simple scale-up. Reagent-grade and affordable dietary supplement-grade ellagic acid was sourced from tree bark and pomegranate hulls, respectively. Biocompatibility and colloidal stability were confirmed by in vitro assays. The material exhibits remarkable chemical stability for a bioinspired MOF (pH = 2-14, hydrothermal conditions, heated organic solvents, biological media, SO2 and H2 S), attributed to the strongly chelating phenolates. A total H2 S uptake of 15.95 mmol g-1 was recorded, representing one of the highest H2 S capacities for a MOF, where polysulfides are formed inside the pores of the material. Phenolic phytochemicals remain largely unexplored as linkers for MOF synthesis, opening new avenues to design stable, eco-friendly, scalable, and low-cost MOFs for diverse applications, including drug delivery.- Published
- 2020
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24. A Tetratopic Phosphonic Acid for the Synthesis of Permanently Porous MOFs: Reactor Size-Dependent Product Formation and Crystal Structure Elucidation via Three-Dimensional Electron Diffraction.
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Wöhlbrandt S, Meier C, Reinsch H, Svensson Grape E, Inge AK, and Stock N
- Abstract
Following the strategy of installing porosity in coordination polymers predefined by linker geometry, we employed the new tetratopic linker molecule 1,1,2,2-tetrakis[4-phosphonophenyl]ethylene (H
8 TPPE) for the synthesis of new porous metal phosphonates. A high-throughput study was carried out using Ni2+ and Co2+ as metal ions, and a very strong influence of the reactor size on the product formation is observed while maintaining the same reaction parameters. Using small autoclaves ( V = 250 μL), single crystals of isostructural mononuclear complexes of the composition [Ni(H3 DPBP)2 (H2 O)4 ] ( 1 ) and [Co(H3 DPBP)2 (H2 O)4 ] ( 2 ) are formed. They contain the linker molecule H4 DPBP (4,4'-diphosphonobenzophenone), which is formed in situ by oxidation of H8 TPPE. Using autoclaves with a volume of V = 2 mL, two new 3D metal-organic frameworks (MOFs) of composition [Ni2 (H4 TPPE)(H2 O)6 ]·4H2 O (CAU-46) and [Co2 (H4 TPPE)(H2 O)4 ]·3H2 O (CAU-47) were isolated in bulk quantities, and their crystal structures were determined from three-dimensional electron diffraction (3D ED) and powder X-ray diffraction data. Using even larger autoclaves ( V = 30 mL), another 3D MOF of the composition [Co2 (H4 TPPE)]·6H2 O (Co-CAU-48) was obtained, and a structure model was established via 3D ED measurements. Remarkably, the isostructural compound [Ni2 (H4 TPPE)]·9H2 O (Ni-CAU-48) is only obtained indirectly, i.e., via thermal activation of CAU-46. As the chosen linker geometry leads to the formation of MOFs, topological analyses were carried out, highlighting the different connectivities observed in the three frameworks. Porosity of the compounds was proven via water sorption experiments, resulting in uptakes of 126 mg/g (CAU-46), 105 mg/g (CAU-47), 210 mg/g (Ni-CAU-48), and 109 mg/g (Co-CAU-48).- Published
- 2020
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25. An Expandable Hydrogen-Bonded Organic Framework Characterized by Three-Dimensional Electron Diffraction.
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Cui P, Svensson Grape E, Spackman PR, Wu Y, Clowes R, Day GM, Inge AK, Little MA, and Cooper AI
- Abstract
A molecular crystal of a 2-D hydrogen-bonded organic framework (HOF) undergoes an unusual structural transformation after solvent removal from the crystal pores during activation. The conformationally flexible host molecule, ABTPA , adapts its molecular conformation during activation to initiate a framework expansion. The microcrystalline activated phase was characterized by three-dimensional electron diffraction (3D ED), which revealed that ABTPA uses out-of-plane anthracene units as adaptive structural anchors. These units change orientation to generate an expanded, lower density framework material in the activated structure. The porous HOF, ABTPA-2 , has robust dynamic porosity (SA
BET = 1183 m2 g-1 ) and exhibits negative area thermal expansion. We use crystal structure prediction (CSP) to understand the underlying energetics behind the structural transformation and discuss the challenges facing CSP for such flexible molecules.- Published
- 2020
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26. Polymorphous Indium Metal-Organic Frameworks Based on a Ferrocene Linker: Redox Activity, Porosity, and Structural Diversity.
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Benecke J, Grape ES, Fuß A, Wöhlbrandt S, Engesser TA, Inge AK, Stock N, and Reinsch H
- Abstract
The metallocene-based linker molecule 1,1'-ferrocenedicarboxylic acid (H
2 FcDC) was used to synthesize four different polymorphs of composition [In(OH)(FeC12 H8 O4 )]. Using conventional solvent-based synthesis methods and varying the synthetic parameters such as metal source, reaction temperature, and solvent, two different MOFs and one 1D-coordination polymer denoted as CAU-43 ( 1 ), In-MIL-53-FcDC_a ( 2 ), and In-FcDC ( 3 ) were obtained. Furthermore, thermal treatment of CAU-43 ( 1 ) at 190 °C under vacuum yielded a new polymorph of 2 , In-MIL-53-FcDC_b ( 4 ). Both MOFs 2 and 4 crystallize in a MIL-53 type structure, but in different space groups C 2/ m for 2 and P 1̅ for 4 . The structures of the four title compounds were determined by single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), or a combination of three-dimensional electron diffraction measurements (3D ED) and PXRD. N2 sorption experiments of 1 , 2 , and 4 showed specific surface areas of 355 m2 g-1 , 110 m2 g-1 , and 140 m2 g-1 , respectively. Furthermore, the electronic properties of the title compounds were characterized via Mössbauer and EPR spectroscopy. All Mössbauer spectra showed the characteristic doublet, proving the persistence of the ferrocene moiety. In the cases of 1 , 3 , and 4 , appreciable impurities of ferrocenium ions could be detected by electron paramagnetic resonance spectroscopy. Cyclovoltammetric experiments were performed to demonstrate the accessible redox activity of the linker molecule of the title compounds. A redox process of FcDC2- with oxidation (between 0.86 and 0.97 V) and reduction wave (between 0.69 and 0.80 V) was observed.- Published
- 2020
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27. A Scandium MOF with an Unprecedented Inorganic Building Unit, Delimiting the Micropore Windows.
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Rönfeldt P, Grape ES, Inge AK, Novikov DV, Khadiev A, Etter M, Rabe T, Benecke J, Terraschke H, and Stock N
- Abstract
A new scandium metal-organic framework (Sc-MOF) with the composition of [Sc(OH)(OBA)], denoted as Sc-CAU-21, was prepared under solvothermal reaction conditions using 4,4'-oxidibenzoic acid (H
2 OBA) as the ligand. Single-crystal structure determination revealed the presence of the new inorganic building unit (IBU) {Sc8 (μ-OH)8 (O2 C)16 }. It is composed of cis-connected ScO6 polyhedra forming an eight-membered ring through bridging μ-OH groups. The connection of the IBUs leads to a 3D framework, containing 1D pores with a diameter between 4.2 and 5.6 Å. Pore access is limited by the size of the IBU, and in contrast to the isoreticular aluminum compound Al-CAU-21 [Al(OH)(OBA)], which is nonporous toward nitrogen at 77 K, Sc-CAU-21 exhibits a specific surface area of 610 m2 g-1 . The title compound is thermally stable in air up to 350 °C and can be employed as a host for photoluminescent ions. Sc-CAU-21 exhibits a ligand-based blue emission, and (co)substituting Sc3+ ions with Ln3+ ions (Eu3+ , Tb3+ , and Dy3+ ) allows the tuning of the emitting color of the phosphor from red to green. Single-phase white-light emission with CIE color coordinates close to the ideal for white-light emission was also achieved. The luminescence property was utilized in combination with powder X-ray diffraction to study in situ the crystallization process of Sc-CAU-21:Tb and Sc-CAU-21:Eu. Both studies indicate a two-step crystallization process, with a crystalline intermediate, prior to the formation of Sc-CAU-21:Ln.- Published
- 2020
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28. Silver-Triggered Activity of a Heterogeneous Palladium Catalyst in Oxidative Carbonylation Reactions.
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Li MB, Yang Y, Rafi AA, Oschmann M, Grape ES, Inge AK, Córdova A, and Bäckvall JE
- Abstract
A silver-triggered heterogeneous Pd-catalyzed oxidative carbonylation has been developed. This heterogeneous process exhibits high efficiency and good recyclability, and was utilized for the one-pot construction of polycyclic compounds with multiple chiral centers. AgOTf was used to remove chloride ions in the heterogeneous catalyst Pd-AmP-CNC, thereby generating highly active Pd
II , which results in high efficiency of the heterogeneous catalytic system., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2020
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29. Metal-Organic Frameworks with Hexakis(4-carboxyphenyl)benzene: Extensions to Reticular Chemistry and Introducing Foldable Nets.
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Amombo Noa FM, Svensson Grape E, Brülls SM, Cheung O, Malmberg P, Inge AK, McKenzie CJ, Mårtensson J, and Öhrström L
- Abstract
Nine metal-organic frameworks have been prepared with the hexagon-shaped linker 1,2,3,4,5,6-hexakis(4-carboxyphenyl)benzene (H
6 cpb) by solvothermal reactions in dimethylformamide (dmf) or dimethylacetamide (dmac) with acetic acid or formic acid as modulators: [Bi2 (cpb)(acetato)2 (dmf)2 ]·2dmf CTH-6 forms a rtl -net; 2(H2 NMe2 )[Cu2 (cpb)] CTH-7 forms a kgd -net; [Fe4 (cpb)(acetato)2 (dmf)4 ] CTH-8 and [Co4 (cpb)(acetato)2 (dmf)4 ] CTH-9 are isostructural and form yav -nets; 2(HNEt3 )[Fe2 (cpb)] CTH-10 and the two polymorphs of 2(H2 NMe2 )[Zn2 (cpb)]·1.5dmac, Zn-MOF-888 and CTH-11 , show kgd -nets; [Cu2 (cpb)(acetato)2 (dmf)2 ]·2dmf, CTH-12 , forms a mixed coordination and hydrogen-bonded sql -net; and 2(H2 NMe2 )[Zn2 (cpb)] CTH-13 , a similarly mixed yav -net. Surface area values (Brunauer-Emmett-Teller, BET) range from 34 m2 g-1 for CTH-12 to 303 m2 g-1 for CTH-9 for samples activated at 120 °C in dynamic vacuum. All compounds show normal (10-fold higher) molar CO2 versus N2 uptake at 298 K, except the 19-fold CO2 uptake for CTH-12 containing Cu(II) dinuclear paddle-wheels. We also show how perfect hexagons and triangles can combine to a new 3D topology laf , a model of which gave us the idea of foldable network topologies , as the laf -net can fold into a 2D form while retaining the local geometry around each vertex. Other foldable nets identified are cds , cds-a , ths , sqc163 , clh , jem , and tfc covering the basic polygons and their combinations. The impact of this concept on "breathing" MOFs is discussed. I2 sorption, both from gas phase and from MeOH solution, into CTH-7 were studied by time of flight secondary ion mass spectrometry (ToF-SIMS) on dried crystals. I2 was shown to have penetrated the crystals, as layers were consecutively peeled off by the ion beam. We suggest ToF-SIMS to be a method for studying sorption depth profiles of MOFs.- Published
- 2020
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30. Highly Diastereoselective Palladium-Catalyzed Oxidative Cascade Carbonylative Carbocyclization of Enallenols.
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Posevins D, Li MB, Svensson Grape E, Inge AK, Qiu Y, and Bäckvall JE
- Abstract
A palladium-catalyzed oxidative cascade carbonylative carbocyclization of enallenols was developed. Under mild reaction conditions, a range of cis -fused [5,5] bicyclic γ-lactones and γ-lactams with a 1,3-diene motif were obtained in good yields with high diastereoselectivity. The obtained lactone/lactam products are viable substrates for a stereoselective Diels-Alder reaction with N -phenylmaleimide, providing polycyclic compounds with increased molecular complexity.
- Published
- 2020
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31. Metal-Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective.
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Pascanu V, González Miera G, Inge AK, and Martín-Matute B
- Abstract
Recent advances in organic chemistry and materials chemistry have enabled the porosity of new materials to be accurately controlled on the nanometer scale. In this context, metal-organic frameworks (MOFs) have rapidly become one of the most attractive classes of solid supports currently under investigation in heterogeneous catalysis. Their unprecedented degree of tunability gives MOFs the chance to succeed where others have failed. The past decade has witnessed an exponential growth in the complexity of new structures. MOFs with a variety of topologies and pore sizes show excellent stability across wide ranges of pH and temperature. Even the controlled insertion of defects, to alter the MOF's properties in a predictable manner, has become commonplace. However, research on catalysis with MOFs has been sluggish in catching up with modern trends in organic chemistry. Relevant issues such as enantioselective processes, C-H activation, or olefin metathesis are still rarely discussed. In this Perspective, we highlight meritorious examples that tackle important issues from contemporary organic synthesis, and that provide a fair comparison with existing catalysts. Some of these MOF catalysts already outcompete state-of-the-art homogeneous solutions. For others, improvements may still be required, but they have merit in aiming for the bigger challenge. Furthermore, we also identify some important areas where MOFs are likely to make a difference, by addressing currently unmet needs in catalysis instead of trying to outcompete homogeneous catalysts in areas where they excel. Finally, we strongly advocate for rational design of MOF catalysts, founded on a deep mechanistic understanding of the events taking place inside the pore.
- Published
- 2019
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32. A Porous Cobalt Tetraphosphonate Metal-Organic Framework: Accurate Structure and Guest Molecule Location Determined by Continuous-Rotation Electron Diffraction.
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Wang B, Rhauderwiek T, Inge AK, Xu H, Yang T, Huang Z, Stock N, and Zou X
- Abstract
Single-crystal electron diffraction has shown to be powerful for structure determination of nano- and submicron-sized crystals that are too small to be studied by single-crystal X-ray diffraction. However, it has been very challenging to obtain high quality electron diffraction data from beam sensitive crystals such as metal-organic frameworks (MOFs). It is even more difficult to locate guest species in the pores of MOF crystals. Here, we present synthesis of a novel porous cobalt MOF with 1D channels, [Co
2 (Ni-H4 TPPP)]⋅2 DABCO⋅6 H2 O, (denoted Co-CAU-36; DABCO=1,4-diazabicyclo[2.2.2]octane), and its structure determination using continuous rotation electron diffraction (cRED) data. By combining a fast hybrid electron detector with low sample temperature (96 K), high resolution (0.83-1.00 Å) cRED data could be obtained from eight Co-CAU-36 crystals. Independent structure determinations were conducted using each of the eight cRED datasets. We show that all atoms in the MOF framework could be located. More importantly, we demonstrate for the first time that organic molecules in the pores, which were previously difficult to find, could be located using the cRED data. A comparison of eight independent structure determinations using different datasets shows that structural models differ only on average by 0.03(2) Å for the framework atoms and 0.10(6) and 0.16(12) Å for DABCO and water molecules, respectively., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2018
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33. Chemodivergent and Diastereoselective Synthesis of γ-Lactones and γ-Lactams: A Heterogeneous Palladium-Catalyzed Oxidative Tandem Process.
- Author
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Li MB, Inge AK, Posevins D, Gustafson KPJ, Qiu Y, and Bäckvall JE
- Abstract
A palladium-catalyzed oxidative tandem process of enallenols was accomplished within a homogeneous/heterogeneous catalysis manifold, setting the stage for the highly chemodivergent and diastereoselective synthesis of γ-lactones and γ-lactams under mild conditions.
- Published
- 2018
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34. Multistimuli-Responsive Enaminitrile Molecular Switches Displaying H + -Induced Aggregate Emission, Metal Ion-Induced Turn-On Fluorescence, and Organogelation Properties.
- Author
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Ren Y, Xie S, Svensson Grape E, Inge AK, and Ramström O
- Abstract
Multistimuli-responsive enaminitrile-based configurational switches displaying aggregation-induced emission (AIE), fluorescence turn-on effects, and supergelation properties are presented. The E-isomers dominated (>97%) in neutral/basic solution, and the structures underwent precisely controlled switching around the enamine C═C bond upon addition of acid/base. Specific fluorescence output was observed in response to different external input in the solution and solid states. In response to H
+ , configurational switching resulted in complete formation of the nonemissive Z-H+ -isomers in solution, however displaying deep-blue to blue fluorescence (ΦF up to 0.41) in the solid state. In response to CuII in the solution state, the E-isomers exhibited intense, turn-on, blue-green fluorescence, which could be turned off by addition of competitive coordination. The acid/base-activated switching, together with the induced AIE-effects, further enabled the accomplishment of a responsive superorganogelator. In nonpolar solvents, a blue-fluorescent supramolecular gel was formed upon addition of acid to the E-isomer suspension. The gelation could be reversed by addition of base, and the overall, reversible process could be repeated at least five cycles.- Published
- 2018
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35. Design and synthesis of dopant-free organic hole-transport materials for perovskite solar cells.
- Author
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Wang L, Zhang J, Liu P, Xu B, Zhang B, Chen H, Inge AK, Li Y, Wang H, Cheng YB, Kloo L, and Sun L
- Abstract
Two novel dopant-free hole-transport materials (HTMs) with spiro[dibenzo[c,h]xanthene-7,9'-fluorene] (SDBXF) skeletons were prepared via facile synthesis routes. A power conversion efficiency of 15.9% in perovskite solar cells is attained by using one HTM without dopants, which is much higher than undoped Spiro-OMeTAD-based devices (10.8%). The crystal structures of both new HTMs were systematically investigated to reveal the reasons behind such differences in performance and to indicate the design principles of more advanced HTMs.
- Published
- 2018
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36. Probing the Evolution of Palladium Species in Pd@MOF Catalysts during the Heck Coupling Reaction: An Operando X-ray Absorption Spectroscopy Study.
- Author
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Yuan N, Pascanu V, Huang Z, Valiente A, Heidenreich N, Leubner S, Inge AK, Gaar J, Stock N, Persson I, Martín-Matute B, and Zou X
- Abstract
The mechanism of the Heck C-C coupling reaction catalyzed by Pd@MOFs has been investigated using operando X-ray absorption spectroscopy (XAS) and powder X-ray diffraction (PXRD) combined with transmission electron microscopy (TEM) analysis and nuclear magnetic resonance (
1 H NMR) kinetic studies. A custom-made reaction cell was used, allowing operando PXRD and XAS data collection using high-energy synchrotron radiation. By analyzing the XAS data in combination with ex situ studies, the evolution of the palladium species is followed from the as-synthesized to its deactivated form. An adaptive reaction mechanism is proposed. Mononuclear Pd(II) complexes are found to be the dominant active species at the beginning of the reaction, which then gradually transform into Pd nanoclusters with 13-20 Pd atoms on average in later catalytic turnovers. Consumption of available reagent and substrate leads to coordination of Cl- ions to their surfaces, which causes the poisoning of the active sites. By understanding the deactivation process, it was possible to tune the reaction conditions and prolong the lifetime of the catalyst.- Published
- 2018
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37. A multi-purpose reaction cell for the investigation of reactions under solvothermal conditions.
- Author
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Heidenreich N, Rütt U, Köppen M, Inge AK, Beier S, Dippel AC, Suren R, and Stock N
- Abstract
A new versatile and easy-to-use remote-controlled reactor setup aimed at the analysis of chemical reactions under solvothermal conditions has been constructed. The reactor includes a heating system that can precisely control the temperature inside the reaction vessels in a range between ambient temperature and 180 °C. As reaction vessels, two sizes of commercially available borosilicate vessels (V
max = 5 and 11 ml) can be used. The setup furthermore includes the option of stirring and injecting of up to two liquid additives or one solid during the reaction to initiate very fast reactions, quench reactions, or alter chemical parameters. In addition to a detailed description of the general setup and its functionality, three examples of studies conducted using this setup are presented.- Published
- 2017
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38. Design and synthesis of theranostic antibiotic nanodrugs that display enhanced antibacterial activity and luminescence.
- Author
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Xie S, Manuguri S, Proietti G, Romson J, Fu Y, Inge AK, Wu B, Zhang Y, Häll D, Ramström O, and Yan M
- Subjects
- Anti-Bacterial Agents chemical synthesis, Anti-Infective Agents chemical synthesis, Anti-Infective Agents pharmacology, Bacteria drug effects, Drug Design, Drug Resistance, Bacterial, Fluoroquinolones chemistry, Luminescence, Microbial Sensitivity Tests, Theranostic Nanomedicine, Ciprofloxacin analogs & derivatives, Ciprofloxacin chemical synthesis, Ciprofloxacin pharmacology
- Abstract
We report the modular formulation of ciprofloxacin-based pure theranostic nanodrugs that display enhanced antibacterial activities, as well as aggregation-induced emission (AIE) enhancement that was successfully used to image bacteria. The drug derivatives, consisting of ciprofloxacin, a perfluoroaryl ring, and a phenyl ring linked by an amidine bond, were efficiently synthesized by a straightforward protocol from a perfluoroaryl azide, ciprofloxacin, and an aldehyde in acetone at room temperature. These compounds are propeller-shaped, and upon precipitation into water, readily assembled into stable nanoaggregates that transformed ciprofloxacin derivatives into AIE-active luminogens. The nanoaggregates displayed increased luminescence and were successfully used to image bacteria. In addition, these nanodrugs showed enhanced antibacterial activities, lowering the minimum inhibitory concentration (MIC) by more than one order of magnitude against both sensitive and resistant Escherichia coli The study represents a strategy in the design and development of pure theranostic nanodrugs for combating drug-resistant bacterial infections., Competing Interests: The authors declare no conflict of interest.
- Published
- 2017
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39. Elucidation of the elusive structure and formula of the active pharmaceutical ingredient bismuth subgallate by continuous rotation electron diffraction.
- Author
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Wang Y, Takki S, Cheung O, Xu H, Wan W, Öhrström L, and Inge AK
- Subjects
- Gallic Acid chemistry, Molecular Structure, Electrons, Gallic Acid analogs & derivatives, Organometallic Compounds chemistry, Pharmaceutical Preparations chemistry, Rotation
- Abstract
Bismuth subgallate has been used in wound and gastrointestinal therapy for over a century. The combination of continuous rotation electron diffraction and sample cooling finally revealed its structure as a coordination polymer. The structure provides insight regarding its formula, poor solubility, acid resistance and previously unreported gas sorption properties.
- Published
- 2017
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40. Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization.
- Author
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Krüger M, Inge AK, Reinsch H, Li YH, Wahiduzzaman M, Lin CH, Wang SL, Maurin G, and Stock N
- Abstract
The in situ and systematic high-throughput investigation of the system Al
3+ /4,4'-benzophenonedicarboxylic acid (H2 BPDC)/DMF/H2 O in the presence of various additives was carried out, and a new Al-MOF of composition [Al(OH)(BPDC)], denoted as CAU-21-BPDC, was obtained. Its crystal structure was determined from single-crystal X-ray diffraction data (space group I422, a = b = 17.2528(7) Å, c = 23.864(1) Å). The structure is built up by octanuclear rings of cis corner-sharing AlO6 polyhedra forming the inorganic building unit (IBU). These {Al8 O8 } IBUs are arranged in a bcu packing and connected via BPDC2- ions in a way that each IBU is linked via two linker molecules to each of the eight adjacent IBUs. Thus, accessible, one-dimensional modulated pores with a diameter between 3.6 and 6.5 Å are formed. In addition, tetrahedral cavities are formed by the BPDC2- linker molecules. The framework of CAU-21-BPDC is polymorphous with that of CAU-8-BPDC, which contains one-dimensional chains of trans corner-sharing AlO6 polyhedra connected by BPDC2- ions. Replacing H2 BPDC by 4,4'-oxydibenzoic acid (H2 ODB), which contains an oxygen atom between the phenyl rings instead of a keto group, leads to the synthesis of Al-MOFs isoreticular with CAU-8-BPDC and CAU-21-BPDC. In addition, a coordination polymer, [Al(HODB)2 (OH)], was discovered and structurally characterized. The structure of CAU-8-ODB was refined from powder X-ray diffraction data, while a Pawley refinement was carried out for CAU-21-ODB to determine the lattice parameters and confirm phase purity. The structure of CAU-21-ODB was confirmed using density functional theory (DFT) calculations. A thorough characterization shows that the CAU-8 and CAU-21-type structures are stable up to 350 and 300 °C in air, respectively, almost independent of the linker molecules incorporated. The former MOFs are porous toward N2 and CO2 , while the latter only adsorb CO2 .- Published
- 2017
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41. Dihydroxybenzoquinone as Linker for the Synthesis of Permanently Porous Aluminum Metal-Organic Frameworks.
- Author
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Halis S, Inge AK, Dehning N, Weyrich T, Reinsch H, and Stock N
- Abstract
Two new dihydroxybenzoquinone-based metal-organic frameworks, ((CH3)2NH2)3[Al4(L1)3(L1(•))3]·3DMF (1, denoted CAU-20) and ((CH3)2NH2)3[Al4(L2)3(L2(•))3]·9DMF (2, denoted CAU-20-Cl2), were synthesized at 120 °C in DMF using 2,5-dihydroxy-p-benzoquinone ((C6H2(OH)2(O)2), H2L1) and 2,5-dichloro-3,6-dihydroxy-p-benzoquinone ((C6Cl2(OH)2(O)2), H2L2), respectively. Compared to other Al-MOFs, which contain carboxylate or phosphonate groups that connect the metal sites, in 1 and 2 the Al(3+) are coordinated by oxido groups. The metal ions are octahedrally surrounded by oxygen atoms of the deprotonated linker molecules to generate honeycomb layers with a metal to linker ratio of Al: L1/L2 = 2:3. The layers contain L1(2-) and L2(2-) ions as well as linker radical ions L1(•3-) and L2(•3-) in a molar ratio of 1 to 1. The presence of radical ions was confirmed by EPR and UV-vis-spectroscopic measurements, and the composition was determined from a combination of PXRD, (1)H NMR, TG, and elemental analyses. Charge balance is accomplished through intercalation of (CH3)2NH2(+) ions which are formed by partial hydrolysis of DMF. In the structures of 1 and 2 the eclipsed layers are AA and ABAB stacked, respectively, and one-dimensional hexagonal channels with diameters of ca. 9 and 6 Å are formed. Both compounds exhibit permanent porosity and have specific surface areas of 1440 and 1430 m(2) g(-1), respectively.
- Published
- 2016
- Full Text
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42. Unprecedented Topological Complexity in a Metal-Organic Framework Constructed from Simple Building Units.
- Author
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Inge AK, Köppen M, Su J, Feyand M, Xu H, Zou X, O'Keeffe M, and Stock N
- Abstract
A bismuth-based metal-organic framework (MOF), [Bi(BTC)(H2O)]·2H2O·MeOH denoted CAU-17, was synthesized and found to have an exceptionally complicated structure with helical Bi-O rods cross-linked by 1,3,5-benzenetricarboxylate (BTC(3-)) ligands. Five crystallographically independent 1D channels including two hexagonal channels, two rectangular channels, and one triangular channel have accessible diameters of 9.6, 9.6, 3.6, 3.6, and 3.4 Å, respectively. The structure is further complicated by twinning. Rod-incorporated MOF structures typically have underlying nets with only one unique node and three or four unique edges. In contrast, topological analysis of CAU-17 revealed unprecedented complexity for a MOF structure with 54 unique nodes and 135 edges. The complexity originates from the rod packing and the rods themselves, which are related to aperiodic helices.
- Published
- 2016
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43. New Al-MOFs based on sulfonyldibenzoate ions: a rare example of intralayer porosity.
- Author
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Reimer N, Reinsch H, Inge AK, and Stock N
- Abstract
A new sulfone-functionalized metal-organic framework [Al(OH)(SDBA)]·0.25DMF, denoted CAU-11, was synthesized using a V-shaped linker molecule 4,4'-sulfonyldibenzoic acid (H2SDBA). The crystal structure was solved from synchrotron X-ray powder diffraction data. Chains of trans corner-sharing AlO6 octahedra are interconnected by the carboxylate groups to form layers (ABAB stacking). Within the layers, hydrophobic lozenge-shaped pores with a diameter of 6.4 × 7.1 Å(2) are present inducing permanent porosity (aBET = 350 m(2) g(-1) and Vmicro = 0.17 cm(3) g(-1)). With the application of HT-methods (HT = high throughput), the isoreticular carboxylate functionalized compound [Al(OH)(H2DPSTC)]·0.5H2O (CAU-11-COOH) was synthesized using the linker molecule 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DPSDA), which hydrolyzes under the reaction conditions. Due to the additional noncoordinating carboxylic acid groups the pores are hydrophilic. Changing the molar ratio of Al(3+) to linker lead to the discovery of a second new compound [Al2(OH)2(DPSTC)(H2O)2]·0.5H2O (CAU-12). In CAU-12 the linker molecule is fully deprotonated which leads to different connectivity compared to the structure of CAU-11-COOH. Thermal activation of CAU-12 leads to dehydration and transformation of the structure to [Al2(OH)2(DPSTC)]·nH2O (CAU-12-dehy). Coordinated water molecules were removed, and the coordination site is replaced by the previously noncoordinating O atom of the adjacent carboxylate group. The SO2-groups point into the pores resulting in a highly hydrophobic three-dimensional framework. The compounds exhibit high thermal stability in air at least up to 420 °C. Synthesis of CAU-11 can be easily scaled up in very high yields (98%).
- Published
- 2015
- Full Text
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44. Insights into Ru-based molecular water oxidation catalysts: electronic and noncovalent-interaction effects on their catalytic activities.
- Author
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Duan L, Wang L, Inge AK, Fischer A, Zou X, and Sun L
- Abstract
A series of Ru-bda water oxidation catalysts [Ru(bda)L2] (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; L = [HNEt3][3-SO3-pyridine], 1; 4-(EtOOC)-pyridine, 2; 4-bromopyridine, 3; pyridine, 4; 4-methoxypyridine, 5; 4-(Me2N)-pyridine, 6; 4-[Ph(CH2)3]-pyridine, 7) were synthesized with electron-donating/-withdrawing groups and hydrophilic/hydrophobic groups in the axial ligands. These complexes were characterized by (1)H NMR spectroscopy, high-resolution mass spectrometry, elemental analysis, and electrochemistry. In addition, complexes 1 and 6 were further identified by single crystal X-ray crystallography, revealing a highly distorted octahedral configuration of the Ru coordination sphere. All of these complexes are highly active toward Ce(IV)-driven (Ce(IV) = Ce(NH4)2(NO3)6) water oxidation with oxygen evolution rates up to 119 mols of O2 per mole of catalyst per second. Their structure-activity relationship was investigated. Electron-withdrawing and noncovalent interactions (attraction) exhibit positive effect on the catalytic activity of Ru-bda catalysts.
- Published
- 2013
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45. Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand.
- Author
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Tong L, Inge AK, Duan L, Wang L, Zou X, and Sun L
- Subjects
- Anions chemistry, Catalysis, Crystallography, X-Ray, Electrochemical Techniques, Ligands, Models, Molecular, Molecular Conformation, Organometallic Compounds chemical synthesis, Oxidation-Reduction, Organometallic Compounds chemistry, Ruthenium chemistry, Water chemistry
- Abstract
Mononuclear Ru-based water oxidation catalysts containing anionic ancillary ligands have shown promising catalytic efficiency and intriguing properties. However, their insolubility in water restricts a detailed mechanism investigation. In order to overcome this disadvantage, complexes [Ru(II)(bpc)(bpy)OH2](+) (1(+), bpc = 2,2'-bipyridine-6-carboxylate, bpy = 2,2'-bipyridine) and [Ru(II)(bpc)(pic)3](+) (2(+), pic = 4-picoline) were prepared and fully characterized, which features an anionic tridentate ligand and has enough solubility for spectroscopic study in water. Using Ce(IV) as an electron acceptor, both complexes are able to catalyze O2-evolving reaction with an impressive rate constant. On the basis of the electrochemical and kinetic studies, a water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS. Meanwhile, an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. The effect of anionic ligand regarding catalytic water oxidation was discussed explicitly in comparison with previously reported mononuclear Ru catalysts carrying neutral tridentate ligands, for example, 2,2':6',2″-terpyridine (tpy). When 2(+) was oxidized to the trivalent state, one of its picoline ligands dissociated from the Ru center. The rate constant of picoline dissociation was evaluated from time-resolved UV-vis spectra.
- Published
- 2013
- Full Text
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46. A highly active bifunctional iridium complex with an alcohol/alkoxide-tethered N-heterocyclic carbene for alkylation of amines with alcohols.
- Author
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Bartoszewicz A, Marcos R, Sahoo S, Inge AK, Zou X, and Martín-Matute B
- Abstract
A series of new iridium(III) complexes containing bidentate N-heterocyclic carbenes (NHC) functionalized with an alcohol or ether group (NHC-OR, R = H, Me) were prepared. The complexes catalyzed the alkylation of anilines with alcohols as latent electrophiles. In particular, biscationic Ir(III) complexes of the type [Cp*(NHC-OH)Ir(MeCN)](2+)2[BF(4)(-)] afforded higher-order amine products with very high efficiency; up to >99% yield using a 1:1 ratio of reactants and 1-2.5 mol % of Ir, in short reaction times (2-16 h) and under base-free conditions. Quantitative yields were also obtained at 50 °C, although longer reaction times (48-60 h) were needed. A large variety of aromatic amines have been alkylated with primary and secondary alcohols. The reactivity of structurally related iridium(III) complexes was also compared to obtain insights into the mechanism and into the structure of possible catalytic intermediates. The Ir(III) complexes were stable towards oxygen and moisture, and were characterized by NMR, HRMS, single-crystal X-ray diffraction, and elemental analyses., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2012
- Full Text
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47. SU-75: a disordered Ge10 germanate with pcu topology.
- Author
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Huang S, Inge AK, Yang S, Christensen KE, Zou X, and Sun J
- Abstract
A disordered open-framework germanate, denoted as SU-75, was synthesized under hydrothermal conditions using diethylenetriamine (dien) or alternatively 1,4-diaminobutane (dab) as the structure directing agent (SDA). SU-75 crystallizes in a tetragonal space group I42d (No. 122) with a = 18.145(3) Å and c = 41.701(9) Å. The three-dimensional (3D) framework is built from Ge(10)(O,OH)(28) (Ge(10)) clusters that are connected following the pcu (primitive cubic) net topology. SU-75 has 10-, 11- and 12-ring channels along the a- and b-axes and channels with alternating 8-, 10-, 12-, 10-ring openings along the c-axis. The framework exhibits a serious disorder, resulted from two possible connectivities between the units of four Ge(10) clusters (4Ge(10) unit). The chemical formula of SU-75 is |(H(2)SDA)(2)(H(2)O)(n)|[Ge(10)O(21)(OH)(2)] (SDA = dien or dab, n = 5-6), determined by combining single crystal synchrotron X-ray diffraction, thermogravimetric analysis (TGA) and CHN elemental analysis. A superoctahedron is introduced to simplify the description of the connectivity of the Ge(10) clusters and to illustrate the disorder. This is also used to compare the structure of SU-75 with those of related Ge(10) germanates.
- Published
- 2012
- Full Text
- View/download PDF
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