Hydrophobicity and dielectric properties across an isostructural family of MOFs: a duet or a duel?

An isoreticular family of metal-organic frameworks is post-synthetically subjected to polymer grafting. Surface hydrophobicity analysis, adsorption experiments, and impedance spectroscopy characterise the water molecules adsorbed, both on the surface and in the pores, while resolving how molecular mobility is impacted

Metal-Organic Frameworks in Germany: from Synthesis to Function

Metal-organic frameworks (MOFs) are constructed from a combination of inorganic and organic units to produce materials which display high porosity, among other unique and exciting properties. MOFs have shown promise in many wide-ranging applications, such as catalysis and gas separations. In this review, we highlight MOF research conducted by Germany-based research groups. Specifically, we feature approaches for the synthesis of new MOFs, high-throughput MOF production, advanced characterization methods and examples of advanced functions and properties

Flexible metal–organic frameworks

Advances in flexible and functional metal–organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009–2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host–guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal–organic frameworks for separation, catalysis, sensing, and biomedicine

Continuous infusion of an agonist of the tumor necrosis factor receptor 2 in the spinal cord improves recovery after traumatic contusive injury.

AimThe activation of the TNFR2 receptor is beneficial in several pathologies of the central nervous system, and this study examines whether it can ameliorate the recovery process following spinal cord injury.MethodsEHD2-sc-mTNFR2 , an agonist specific for TNFR2, was used to treat neurons exposed to high levels of glutamate in vitro. In vivo, it was infused directly to the spinal cord via osmotic pumps immediately after a contusion to the cord at the T9 level. Locomotion behavior was assessed for 6 weeks, and the tissue was analyzed (lesion size, RNA and protein expression, cell death) after injury. Somatosensory evoked potentials were also measured in response to hindlimb stimulation.ResultsThe activation of TNFR2 protected neurons from glutamate-mediated excitotoxicity through the activation of phosphoinositide-3 kinase gamma in vitro and improved the locomotion of animals following spinal cord injury. The extent of the injury was not affected by infusing EHD2-sc-mTNFR2 , but higher levels of neurofilament H and 2', 3'-cyclic-nucleotide 3'-phosphodiesterase were observed 6 weeks after the injury. Finally, the activation of TNFR2 after injury increased the neural response recorded in the cortex following hindlimb stimulation.ConclusionThe activation of TNFR2 in the spinal cord following contusive injury leads to enhanced locomotion and better cortical responses to hindlimb stimulation

Real-time monitoring of cell surface protein arrival with split luciferases

Each cell in a multicellular organism permanently adjusts the concentration of its cell surface proteins. In particular, epithelial cells tightly control the number of carriers, transporters and cell adhesion proteins at their plasma membrane. However, sensitively measuring the cell surface concentration of a particular protein of interest in live cells and in real time represents a considerable challenge. Here, we introduce a novel approach based on split luciferases, which uses one luciferase fragment as a tag on the protein of interest and the second fragment as a supplement to the extracellular medium. Once the protein of interest arrives at the cell surface, the luciferase fragments complement and generate luminescence. We compared the performance of split Gaussia luciferase and split Nanoluciferase by using a system to synchronize biosynthetic trafficking with conditional aggregation domains. The best results were achieved with split Nanoluciferase, for which luminescence increased more than 6000-fold upon recombination. Furthermore, we showed that our approach can separately detect and quantify the arrival of membrane proteins at the apical and basolateral plasma membrane in single polarized epithelial cells by detecting the luminescence signals with a microscope, thus opening novel avenues for characterizing the variations in trafficking in individual epithelial cells

Pd@UiO-66-Type MOFs Prepared by Chemical Vapor Infiltration as Shape-Selective Hydrogenation Catalysts

[EN] Host-guest inclusion properties of UiO-66 and UiO-67 metal-organic frameworks have been studied using ferrocene (FeCp2) as probe molecule. According to variable-temperature solid-state H-1 and C-13 CP-MAS-NMR, two different environments exist for adsorbed FeCp2 inside UiO-66 and UiO-67, which have been assigned to octahedral and tetrahedral cavities. At room temperature, a rapid exchange between these two adsorption sites occurs in UiO-67, while at -80 degrees C the intracrystalline traffic of FeCp2 through the triangular windows is largely hindered. In UiO-66, FeCp2 diffusion is already impeded at room temperature, in agreement with the smaller pore windows. Palladium nanoparticles (Pd NPs) encapsulated inside UiO-66 and UiO-67 have been prepared by chemical vapor infiltration of (allyl)Pd(Cp) followed by UV light irradiation. Infiltration must be carried out at low temperature (-10 degrees C) to avoid uncontrolled decomposition of the organometallic precursor and formation of Pd NPs at the external surface of the MOF. The resulting Pd-MOFs are shape selective catalysts, as shown for the hydrogenation of carbonyl compounds with different steric hindrance.Financial support from the Consolider-Ingenio 2010 (project MULTICAT), the Severo Ochoa program, and the Spanish Ministry of Science and Innovation (project MAT2011-29020-C02-01) is gratefully acknowledged. C. R. is grateful for a graduate student fellowship awarded by the Cluster of Excellence RESOLV (EXC 1069) funded by the German Deutsche Forschungsgemeinschaft (DFG). This project has further received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skolodowska-Curie grant agreement, number 641887.Luz Mínguez, I.; Roesler, C.; Epp, K.; Llabrés I Xamena, FX.; Fischer, RA. (2015). Pd@UiO-66-Type MOFs Prepared by Chemical Vapor Infiltration as Shape-Selective Hydrogenation Catalysts. European Journal of Inorganic Chemistry. 23:3904-3912. https://doi.org/10.1002/ejic.201500299S3904391223Corma, A., García, H., & Llabrés i Xamena, F. X. (2010). Engineering Metal Organic Frameworks for Heterogeneous Catalysis. Chemical Reviews, 110(8), 4606-4655. doi:10.1021/cr9003924Farrusseng, D., Aguado, S., & Pinel, C. (2009). Metal-Organic Frameworks: Opportunities for Catalysis. Angewandte Chemie International Edition, 48(41), 7502-7513. doi:10.1002/anie.200806063Gascon, J., Corma, A., Kapteijn, F., & Llabrés i Xamena, F. X. (2013). Metal Organic Framework Catalysis: Quo vadis? ACS Catalysis, 4(2), 361-378. doi:10.1021/cs400959kLlabres i Xamena, F., & Gascon, J. (Eds.). (2013). Metal Organic Frameworks as Heterogeneous Catalysts. Catalysis Series. doi:10.1039/9781849737586Li, B., Wang, H., & Chen, B. (2014). Microporous Metal-Organic Frameworks for Gas Separation. Chemistry - An Asian Journal, 9(6), 1474-1498. doi:10.1002/asia.201400031Li, J.-R., Kuppler, R. J., & Zhou, H.-C. (2009). Selective gas adsorption and separation in metal–organic frameworks. Chemical Society Reviews, 38(5), 1477. doi:10.1039/b802426jKreno, L. E., Leong, K., Farha, O. K., Allendorf, M., Van Duyne, R. P., & Hupp, J. T. (2011). Metal–Organic Framework Materials as Chemical Sensors. Chemical Reviews, 112(2), 1105-1125. doi:10.1021/cr200324tEsken, D., Turner, S., Lebedev, O. I., Van Tendeloo, G., & Fischer, R. A. (2010). Au@ZIFs: Stabilization and Encapsulation of Cavity-Size Matching Gold Clusters inside Functionalized Zeolite Imidazolate Frameworks, ZIFs. Chemistry of Materials, 22(23), 6393-6401. doi:10.1021/cm102529cHermes, S., Schröter, M.-K., Schmid, R., Khodeir, L., Muhler, M., Tissler, A., … Fischer, R. A. (2005). Metal@MOF: Loading of Highly Porous Coordination Polymers Host Lattices by Metal Organic Chemical Vapor Deposition. Angewandte Chemie International Edition, 44(38), 6237-6241. doi:10.1002/anie.200462515Meilikhov, M., Yusenko, K., Esken, D., Turner, S., Van Tendeloo, G., & Fischer, R. A. (2010). Metals@MOFs - Loading MOFs with Metal Nanoparticles for Hybrid Functions. European Journal of Inorganic Chemistry, 2010(24), 3701-3714. doi:10.1002/ejic.201000473Schröder, F., Esken, D., Cokoja, M., van den Berg, M. W. E., Lebedev, O. I., Van Tendeloo, G., … Fischer, R. A. (2008). Ruthenium Nanoparticles inside Porous [Zn4O(bdc)3] by Hydrogenolysis of Adsorbed [Ru(cod)(cot)]: A Solid-State Reference System for Surfactant-Stabilized Ruthenium Colloids. Journal of the American Chemical Society, 130(19), 6119-6130. doi:10.1021/ja078231uRösler, C., Esken, D., Wiktor, C., Kobayashi, H., Yamamoto, T., Matsumura, S., … Fischer, R. A. (2014). Encapsulation of Bimetallic Nanoparticles into a Metal-Organic Framework: Preparation and Microstructure Characterization of Pd/Au@ZIF-8. European Journal of Inorganic Chemistry, 2014(32), 5514-5521. doi:10.1002/ejic.201402409Müller, M., Hermes, S., Kähler, K., van den Berg, M. W. E., Muhler, M., & Fischer, R. A. (2008). Loading of MOF-5 with Cu and ZnO Nanoparticles by Gas-Phase Infiltration with Organometallic Precursors: Properties of Cu/ZnO@MOF-5 as Catalyst for Methanol Synthesis. Chemistry of Materials, 20(14), 4576-4587. doi:10.1021/cm703339hMüller, M., Zhang, X., Wang, Y., & Fischer, R. A. (2009). Nanometer-sized titania hosted inside MOF-5. Chem. Commun., (1), 119-121. doi:10.1039/b814241fRösler, C., & Fischer, R. A. (2015). Metal–organic frameworks as hosts for nanoparticles. CrystEngComm, 17(2), 199-217. doi:10.1039/c4ce01251hHermannsdörfer, J., Friedrich, M., Miyajima, N., Albuquerque, R. Q., Kümmel, S., & Kempe, R. (2012). Ni/Pd@MIL-101: Synergistic Catalysis with Cavity-Conform Ni/Pd Nanoparticles. Angewandte Chemie International Edition, 51(46), 11473-11477. doi:10.1002/anie.201205078Cirujano, F. G., Llabrés i Xamena, F. X., & Corma, A. (2012). MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst. Dalton Transactions, 41(14), 4249. doi:10.1039/c2dt12480gCirujano, F. G., Leyva-Pérez, A., Corma, A., & Llabrés i Xamena, F. X. (2013). MOFs as Multifunctional Catalysts: Synthesis of Secondary Arylamines, Quinolines, Pyrroles, and Arylpyrrolidines over Bifunctional MIL-101. ChemCatChem, 5(2), 538-549. doi:10.1002/cctc.201200878Guo, Z., Xiao, C., Maligal-Ganesh, R. V., Zhou, L., Goh, T. W., Li, X., … Huang, W. (2014). Pt Nanoclusters Confined within Metal–Organic Framework Cavities for Chemoselective Cinnamaldehyde Hydrogenation. ACS Catalysis, 4(5), 1340-1348. doi:10.1021/cs400982nLi, X., Guo, Z., Xiao, C., Goh, T. W., Tesfagaber, D., & Huang, W. (2014). Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks. ACS Catalysis, 4(10), 3490-3497. doi:10.1021/cs5006635Zhang, W., Lu, G., Cui, C., Liu, Y., Li, S., Yan, W., … Huo, F. (2014). A Family of Metal-Organic Frameworks Exhibiting Size-Selective Catalysis with Encapsulated Noble-Metal Nanoparticles. Advanced Materials, 26(24), 4056-4060. doi:10.1002/adma.201400620Chen, L., Chen, H., Luque, R., & Li, Y. (2014). Metal−organic framework encapsulated Pd nanoparticles: towards advanced heterogeneous catalysts. Chem. Sci., 5(10), 3708-3714. doi:10.1039/c4sc01847hRamsahye, N. A., Gao, J., Jobic, H., Llewellyn, P. L., Yang, Q., Wiersum, A. D., … Maurin, G. (2014). Adsorption and Diffusion of Light Hydrocarbons in UiO-66(Zr): A Combination of Experimental and Modeling Tools. The Journal of Physical Chemistry C, 118(47), 27470-27482. doi:10.1021/jp509672cCatal. Today 2014Cirujano, F. G., Corma, A., & Llabrés i Xamena, F. X. (2015). Conversion of levulinic acid into chemicals: Synthesis of biomass derived levulinate esters over Zr-containing MOFs. Chemical Engineering Science, 124, 52-60. doi:10.1016/j.ces.2014.09.047Vermoortele, F., Ameloot, R., Vimont, A., Serre, C., & De Vos, D. (2011). An amino-modified Zr-terephthalate metal–organic framework as an acid–base catalyst for cross-aldol condensation. Chem. Commun., 47(5), 1521-1523. doi:10.1039/c0cc03038dVermoortele, F., Bueken, B., Le Bars, G., Van de Voorde, B., Vandichel, M., Houthoofd, K., … De Vos, D. E. (2013). Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr). Journal of the American Chemical Society, 135(31), 11465-11468. doi:10.1021/ja405078uVermoortele, F., Vandichel, M., Van de Voorde, B., Ameloot, R., Waroquier, M., Van Speybroeck, V., & De Vos, D. E. (2012). Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks. Angewandte Chemie International Edition, 51(20), 4887-4890. doi:10.1002/anie.201108565McClellan, W. R., Hoehn, H. H., Cripps, H. N., Muetterties, E. L., & Howk, B. W. (1961). π-Allyl Derivatives of Transition Metals. Journal of the American Chemical Society, 83(7), 1601-1607. doi:10.1021/ja01468a013Schaate, A., Roy, P., Godt, A., Lippke, J., Waltz, F., Wiebcke, M., & Behrens, P. (2011). Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals. Chemistry - A European Journal, 17(24), 6643-6651. doi:10.1002/chem.20100321

Electronic transitions of single silicon vacancy centers in the near-infrared spectral region

Photoluminescence (PL) spectra of single silicon vacancy (SiV) centers frequently feature very narrow room temperature PL lines in the near-infrared (NIR) spectral region, mostly between 820 nm and 840 nm, in addition to the well known zero-phonon-line (ZPL) at approx. 738 nm [E. Neu et al., Phys. Rev. B 84, 205211 (2011)]. We here exemplarily prove for a single SiV center that this NIR PL is due to an additional purely electronic transition (ZPL). For the NIR line at 822.7 nm, we find a room temperature linewidth of 1.4 nm (2.6 meV). The line saturates at similar excitation power as the ZPL. ZPL and NIR line exhibit identical polarization properties. Cross-correlation measurements between the ZPL and the NIR line reveal anti-correlated emission and prove that the lines originate from a single SiV center, furthermore indicating a fast switching between the transitions (0.7 ns). g(2) auto-correlation measurements exclude that the NIR line is a vibronic sideband or that it arises due to a transition from/to a meta-stable (shelving) state.Comment: 9 pages, 7 figures, v2 accepted for publication in Phys. Rev.

Reduced thermal expansion by surface-mounted nanoparticles in a pillared-layered metal-organic framework

Control of thermal expansion (TE) is important to improve material longevity in applications with repeated temperature changes or fluctuations. The TE behavior of metal-organic frameworks (MOFs) is increasingly well understood, while the impact of surface-mounted nanoparticles (NPs) on the TE properties of MOFs remains unexplored despite large promises of NP@MOF composites in catalysis and adsorbate diffusion control. Here we study the influence of surface-mounted platinum nanoparticles on the TE properties of Pt@MOF (Pt@Zn2(DP-bdc)2dabco; DP-bdc2-=2,5-dipropoxy-1,4-benzenedicarboxylate, dabco=1,4-diazabicyclo[2.2.2]octane). We show that TE is largely retained at low platinum loadings, while high loading results in significantly reduced TE at higher temperatures compared to the pure MOF. These findings support the chemical intuition that surface-mounted particles restrict deformation of the MOF support and suggest that composite materials exhibit superior TE properties thereby excluding thermal stress as limiting factor for their potential application in temperature swing processes or catalysis

Defect-Engineered Ruthenium MOFs as Versatile Heterogeneous Hydrogenation Catalysts

[EN] Ruthenium MOF [Ru-3(BTC)(2)Y-y] . G(g) (BTC=benzene-1,3,5-tricarboxylate; Y=counter ions=Cl-, OH-, OAc-; G=guest molecules=HOAc, H2O) is modified via a mixed-linker approach, using mixtures of BTC and pyridine-3,5-dicarboxylate (PYDC) linkers, triggering structural defects at the distinct Ru-2 paddlewheel (PW) nodes. This defect-engineering leads to enhanced catalytic properties due to the formation of partially reduced Ru-2-nodes. Application of a hydrogen pre-treatment protocol to the Ru-MOFs, leads to a further boost in catalytic activity. We study the benefits of (1) defect engineering and (2) hydrogen pre-treatment on the catalytic activity of Ru-MOFs in the Meerwein-Ponndorf-Verley reaction and the isomerization of allylic alcohols to saturated ketones. Simple solvent washing could not avoid catalyst deactivation during recycling for the latter reaction, while hydrogen treatment prior to each catalytic run proved to facilitate materials recyclability with constant activity over five runs.Funding by the Spanish Government is acknowledged through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). This project is further funded by the Deutsche Forschungsgemeinschaft grant no. FI-502/32-1 ("DEMOFs"). KE and WRH would like to thank TUM Graduate School and the Gesellschaft Deutscher Chemiker (GDCh) for financial support. KE gratefully acknowledges support from the colleagues Olesia Halbherr (nee Kozachuk) and Wenhua Zhang.Epp, K.; Luz, I.; Heinz, WR.; Rapeyko, A.; Llabrés I Xamena, FX.; Fischer, RA. (2020). Defect-Engineered Ruthenium MOFs as Versatile Heterogeneous Hydrogenation Catalysts. ChemCatChem. 12(6):1720-1725. https://doi.org/10.1002/cctc.201902079S17201725126Gascon, J., Corma, A., Kapteijn, F., & Llabrés i Xamena, F. X. (2013). Metal Organic Framework Catalysis: Quo vadis? ACS Catalysis, 4(2), 361-378. doi:10.1021/cs400959kHasegawa, S., Horike, S., Matsuda, R., Furukawa, S., Mochizuki, K., Kinoshita, Y., & Kitagawa, S. (2007). Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand:  Selective Sorption and Catalysis. Journal of the American Chemical Society, 129(9), 2607-2614. doi:10.1021/ja067374yWang, Z., & Cohen, S. M. (2009). Postsynthetic modification of metal–organic frameworks. Chemical Society Reviews, 38(5), 1315. doi:10.1039/b802258pVermoortele, F., Bueken, B., Le Bars, G., Van de Voorde, B., Vandichel, M., Houthoofd, K., … De Vos, D. E. (2013). Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr). Journal of the American Chemical Society, 135(31), 11465-11468. doi:10.1021/ja405078uZheng, J., Ye, J., Ortuño, M. A., Fulton, J. L., Gutiérrez, O. Y., Camaioni, D. M., … Lercher, J. A. (2019). Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic Framework. Journal of the American Chemical Society, 141(23), 9292-9304. doi:10.1021/jacs.9b02902Rogge, S. M. J., Bavykina, A., Hajek, J., Garcia, H., Olivos-Suarez, A. I., Sepúlveda-Escribano, A., … Gascon, J. (2017). Metal–organic and covalent organic frameworks as single-site catalysts. Chemical Society Reviews, 46(11), 3134-3184. doi:10.1039/c7cs00033bFarrusseng, D., Aguado, S., & Pinel, C. (2009). Metal-Organic Frameworks: Opportunities for Catalysis. Angewandte Chemie International Edition, 48(41), 7502-7513. doi:10.1002/anie.200806063Valvekens, P., Vermoortele, F., & De Vos, D. (2013). Metal–organic frameworks as catalysts: the role of metal active sites. Catalysis Science & Technology, 3(6), 1435. doi:10.1039/c3cy20813cDoonan, C. J., & Sumby, C. J. (2017). Metal–organic framework catalysis. CrystEngComm, 19(29), 4044-4048. doi:10.1039/c7ce90106bDhakshinamoorthy, A., Li, Z., & Garcia, H. (2018). Catalysis and photocatalysis by metal organic frameworks. Chemical Society Reviews, 47(22), 8134-8172. doi:10.1039/c8cs00256hWang, Y., & Wöll, C. (2018). Chemical Reactions at Isolated Single-Sites Inside Metal–Organic Frameworks. Catalysis Letters, 148(8), 2201-2222. doi:10.1007/s10562-018-2432-2Genna, D. T., Pfund, L. Y., Samblanet, D. C., Wong-Foy, A. G., Matzger, A. J., & Sanford, M. S. (2016). Rhodium Hydrogenation Catalysts Supported in Metal Organic Frameworks: Influence of the Framework on Catalytic Activity and Selectivity. ACS Catalysis, 6(6), 3569-3574. doi:10.1021/acscatal.6b00404Chen, H., He, Y., Pfefferle, L. D., Pu, W., Wu, Y., & Qi, S. (2018). Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal-Organic Frameworks in the Aqueous Phase. ChemCatChem, 10(12), 2558-2570. doi:10.1002/cctc.201800211Marx, S., Kleist, W., Huang, J., Maciejewski, M., & Baiker, A. (2010). Tuning functional sites and thermal stability of mixed-linker MOFs based on MIL-53(Al). Dalton Transactions, 39(16), 3795. doi:10.1039/c002483jFang, Z., Bueken, B., De Vos, D. E., & Fischer, R. A. (2015). Defect-Engineered Metal-Organic Frameworks. Angewandte Chemie International Edition, 54(25), 7234-7254. doi:10.1002/anie.201411540Dissegna, S., Epp, K., Heinz, W. R., Kieslich, G., & Fischer, R. A. (2018). Defective Metal-Organic Frameworks. Advanced Materials, 30(37), 1704501. doi:10.1002/adma.201704501Zhang, Y.-B., Furukawa, H., Ko, N., Nie, W., Park, H. J., Okajima, S., … Yaghi, O. M. (2015). Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177. Journal of the American Chemical Society, 137(7), 2641-2650. doi:10.1021/ja512311aDrache, F., Cirujano, F. G., Nguyen, K. D., Bon, V., Senkovska, I., Llabrés i Xamena, F. X., & Kaskel, S. (2018). Anion Exchange and Catalytic Functionalization of the Zirconium-Based Metal–Organic Framework DUT-67. Crystal Growth & Design, 18(9), 5492-5500. doi:10.1021/acs.cgd.8b00832Zhang, W., Kauer, M., Halbherr, O., Epp, K., Guo, P., Gonzalez, M. I., … Fischer, R. A. (2016). Ruthenium Metal-Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties. Chemistry - A European Journal, 22(40), 14297-14307. doi:10.1002/chem.201602641Kozachuk, O., Yusenko, K., Noei, H., Wang, Y., Walleck, S., Glaser, T., & Fischer, R. A. (2011). Solvothermal growth of a ruthenium metal–organic framework featuring HKUST-1 structure type as thin films on oxide surfaces. Chemical Communications, 47(30), 8509. doi:10.1039/c1cc11107hKozachuk, O., Luz, I., Llabrés i Xamena, F. X., Noei, H., Kauer, M., Albada, H. B., … Fischer, R. A. (2014). Multifunctional, Defect-Engineered Metal-Organic Frameworks with Ruthenium Centers: Sorption and Catalytic Properties. Angewandte Chemie International Edition, 53(27), 7058-7062. doi:10.1002/anie.201311128Agirrezabal-Telleria, I., Luz, I., Ortuño, M. A., Oregui-Bengoechea, M., Gandarias, I., López, N., … Soukri, M. (2019). Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts. Nature Communications, 10(1). doi:10.1038/s41467-019-10013-6Zhang, W., Kozachuk, O., Medishetty, R., Schneemann, A., Wagner, R., Khaletskaya, K., … Fischer, R. A. (2015). Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1. European Journal of Inorganic Chemistry, 2015(23), 3913-3920. doi:10.1002/ejic.201500478Heinz, W. R., Kratky, T., Drees, M., Wimmer, A., Tomanec, O., Günther, S., … Fischer, R. A. (2019). Mixed precious-group metal–organic frameworks: a case study of the HKUST-1 analogue [RuxRh3−x(BTC)2]. Dalton Transactions, 48(32), 12031-12039. doi:10.1039/c9dt01198fBäckvall, J.-E. (2002). Transition metal hydrides as active intermediates in hydrogen transfer reactions. Journal of Organometallic Chemistry, 652(1-2), 105-111. doi:10.1016/s0022-328x(02)01316-5Chowdhury, R. L., & Bäckvall, J.-E. (1991). Efficient ruthenium-catalysed transfer hydrogenation of ketones by propan-2-ol. J. Chem. Soc., Chem. Commun., 0(16), 1063-1064. doi:10.1039/c39910001063Ahlsten, N., Bartoszewicz, A., & Martín-Matute, B. (2012). Allylic alcohols as synthetic enolate equivalents: Isomerisation and tandem reactions catalysed by transition metal complexes. Dalton Transactions, 41(6), 1660. doi:10.1039/c1dt11678aAhlsten, N., Lundberg, H., & Martín-Matute, B. (2010). Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature. Green Chemistry, 12(9), 1628. doi:10.1039/c004964fCahard, D., Gaillard, S., & Renaud, J.-L. (2015). Asymmetric isomerization of allylic alcohols. Tetrahedron Letters, 56(45), 6159-6169. doi:10.1016/j.tetlet.2015.09.098Xia, T., Wei, Z., Spiegelberg, B., Jiao, H., Hinze, S., & de Vries, J. G. (2018). Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts. Chemistry - A European Journal, 24(16), 4043-4049. doi:10.1002/chem.201705454Scalambra, F., Lorenzo-Luis, P., de los Rios, I., & Romerosa, A. (2019). Isomerization of allylic alcohols in water catalyzed by transition metal complexes. Coordination Chemistry Reviews, 393, 118-148. doi:10.1016/j.ccr.2019.04.012Yamaguchi, K., Koike, T., Kotani, M., Matsushita, M., Shinachi, S., & Mizuno, N. (2005). Synthetic Scope and Mechanistic Studies of Ru(OH)x/Al2O3-Catalyzed Heterogeneous Hydrogen-Transfer Reactions. Chemistry - A European Journal, 11(22), 6574-6582. doi:10.1002/chem.200500539Mitchell, R. W., Spencer, A., & Wilkinson, G. (1973). Carboxylato-triphenylphosphine complexes of ruthenium, cationic triphenylphosphine complexes derived from them, and their behaviour as homogeneous hydrogenation catalysts for alkenes. Journal of the Chemical Society, Dalton Transactions, (8), 846. doi:10.1039/dt973000084