| 1. |
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| 2. |
- Ahlquist, Mårten, et al.
(author)
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Rhodium(I) hydrogenation in water : Kinetic studies and the detection of an intermediate using C-13{H-1} PHIPNMR spectroscopy
- 2007
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In: Inorganica Chimica Acta. - : Elsevier BV. - 0020-1693 .- 1873-3255. ; 360:5, s. 1621-1627
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Journal article (peer-reviewed)abstract
- The mechanism for hydrogenation of dimethylmaleate in water using cationic rhodium complexes with water-soluble bi-dentate phosphines has been investigated using kinetics and a novel method for the indirect detection of intermediates in catalytic hydrogenation reactions, whereby a late intermediate was detected. A mechanism is proposed involving fast, irreversible substrate binding followed by a rate-determining reaction with dihydrogen.
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| 3. |
- Carson, Fabian, et al.
(author)
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Ruthenium Complexation in an Aluminium Metal-Organic Framework and its Application in Alcohol Oxidation Catalysis
- 2012
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In: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 18:48, s. 15337-15344
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Research review (peer-reviewed)abstract
- A ruthenium trichloride complex has been loaded into an aluminium metalorganic framework (MOF), MOF-253, by post-synthetic modification to give MOF-253-Ru. MOF-253 contains open bipyridine sites that are available to bind with the ruthenium complex. MOF-253-Ru was characterised by elemental analysis, N2 sorption and X-ray powder diffraction. This is the first time that a Ru complex has been coordinated to a MOF through post-synthetic modification and used as a heterogeneous catalyst. MOF-253-Ru catalysed the oxidation of primary and secondary alcohols, including allylic alcohols, with PhI(OAc)2 as the oxidant under very mild reaction conditions (ambient temperature to 40 degrees C). High conversions (up to >99%) were achieved in short reaction times (13 h) by using low catalyst loadings (0.5 mol% Ru). In addition, high selectivities (>90%) for aldehydes were obtained at room temperature. MOF-253-Ru can be recycled up to six times with only a moderate decrease in substrate conversion.
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| 4. |
- Christensen, Kirsten E., et al.
(author)
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An open-framework silicogermanate with 26-ring channels built from seven-coordinated (Ge,Si)10(O, OH)28 clusters
- 2008
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In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 130:12, s. 3758-3759
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Journal article (peer-reviewed)abstract
- We report a new open-framework silicogermanate SU-61 containing 26-ring channels with a low framework density. It can be seen as a crystalline analogue to the mesoporous silica MCM-41. The structure is built from the assembly of (Ge,Si)10(O,OH)28 clusters. It is the first time that silicon has been successfully introduced in the Ge10 cluster in significant amounts (21% of the tetrahedral sites). Five- and six-coordinated Ge10 clusters have previously been observed in other germanate compounds leading to either dense or open structures. In SU-61, the seven-coordinated clusters fall onto yet another underlying net, the osf net. SU-61, along with other Ge10 based frameworks, shows the versatility of the germanate system to adopt defined topologies playing on the connectivity of the clusters following the principles of net decoration and scale chemistry.
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| 5. |
- Christensen, Kirsten E., et al.
(author)
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Open-framework germanates formed by the flexible Ge10 cluster
- 2008
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In: Zeolites and related materials: Trends, targets and challenges. - Amsterdam : Elsevier. - 9780444532978 ; , s. 317-320
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Conference paper (peer-reviewed)abstract
- Open-framework germanates have shown promising results in achieving extra-large pores and channels. Pores that extend to the mesoporous range (>20Å) were reported in SU-M. The structure of SU-M is built by the Ge10X28 (Ge10, X = O, OH, F) clusters. This cluster is also found in Ge-pharmacosiderite, Na4Ge9O20, ICMM-7 and SU-61. The Ge10 cluster has a flexibility to form compounds with both high and very low framework densities.
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| 6. |
- Gustafsson, Mikaela, et al.
(author)
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A Family of Flexible Lanthanide Bipyridinedicarboxylate Metal-Organic Frameworks Showing Reversible Single-Crystal to Single-Crystal Transformations
- 2012
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 12:6, s. 3243-3249
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Journal article (peer-reviewed)abstract
- A family of flexible lanthanide metal-organic frameworks, [Ln(2)(bpydc)(3)(H2O)(3)]center dot nDMF (denoted as SUMOF-6-Ln; Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er, H(2)bpydc =2,2'-bipyridine-5,5'-dicarboxylic acid), was synthesized and characterized. SUMOF-6-Ln has a monoclinic space group P2(1)/c. The three-dimensional framework contains chains of LnO(n) (n = 7-8) polyhedra connected through the bpydc linkers forming 1D rhombic channels along the c-axis. SUMOF-6-Ln showed reversible breathing phenomenon upon desorption/adsorption of the solvent, with up to 27% changes of the unit cell dimensions and 23% changes of the unit cell volume. Single crystal X-ray diffraction (XRD) revealed that the desolvation and resolvation of SUMOF-6-Ln occurred via single-crystal to single-crystal transformations. The thermal behavior of SUMOF-6-Sm was also examined. SUMOF-6-Eu and SUMOF-6-Tb showed solid-state luminescent properties.
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| 7. |
- Gustafsson, Mikaela, 1980-, et al.
(author)
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A family of highly stable lanthanide metal-organic frameworks: structural evolution and catalytic activity
- 2010
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In: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 22:11, s. 3316-3322
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Journal article (peer-reviewed)abstract
- A family of homeotypic porous lanthanide metal−organic frameworks (MOFs), [Ln(btc)(H2O)]·guest (Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Ho (6), Er (7), and Yb (8); guest: DMF or H2O) was synthesized. The structures of the as-synthesized compounds are tetragonal and contain 1D channels with accessible lanthanide ions. In situ single crystal X-ray diffraction shows that 1 undergoes a single-crystal to polycrystalline to single-crystal transformation from room temperature to 180 °C. During the release of DMF and water molecules from the channels by evacuation and subsequent heating, the structures of 1 and 7 transformed from tetragonal to monoclinic, and then to tetragonal, while the structure of 8 remained tetragonal. The transformation between the monoclinic and the low temperature tetragonal phases is reversible. The Ln(btc) MOFs are stable to at least 480 °C and are among the most thermally stable MOFs. The Ln(btc) MOFs act as efficient Lewis acid catalysts for the cyanosilylation of aldehydes yielding cyanohydrins in high yields within short reaction times. 1 also catalyzes the cyanosilylation of less reactive substrates, such as ketones at room temperature. The Ln(btc) MOFs could be recycled and reused without loss of their crystallinity and activity.
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| 8. |
- Gustafsson, Mikaela, et al.
(author)
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A porous chiral lanthanide metal-organic framework with high thermal stability
- 2008
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In: Zeolites and related materials: Trends, targets and challenges. - Amsterdam : Elsevier. - 9780444532978 ; , s. 451-454
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Conference paper (peer-reviewed)abstract
- A metal-organic framework Nd(BTC)(H2O)·DMF (1), which is isostructural with reported Dy(BTC)(H2O)·DMF [1], Tb(BTC)(H2O)1.5·(DMF) (MOF-76) [2] and Eu(BTC)(H2O)·1.5H2O [3], is synthesized. The compound 1 was characterized by SEM/EDS, TGA and in situ PXRD. The structure was determined by single crystal X-ray diffraction. Compound 1 crystallizes in a chiral space group P43, with a = 10.4278(4) and c = 14.2602(12) Å. The structure contains 1D chiral -Nd-O-C-O-Nd- chains linked by the phenyl groups of BTC ligands. The 3D framework contains circular channels along the [001] direction and is stable up to 400°C.
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| 9. |
- Gustafsson, Mikaela, 1980-, et al.
(author)
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Crystal Formation and Size Control of Zeolitic Imidazolate Frameworks with Mixed Imidazolate Linkers
- 2013
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In: Journal of porous materials. - : Springer Science and Business Media LLC. - 1380-2224 .- 1573-4854. ; 20:1, s. 55-63
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Journal article (peer-reviewed)abstract
- The effect of synthesis parameters, such as batch composition and synthesis temperature, on the formationand crystal size of zeolitic imidazolate frameworks(ZIFs) using mixed linkers, imidazole (Im) and benzimidazole(bIm), were studied by X-ray powder diffraction(XRPD) and scanning electron microscopy (SEM). ZIF-7and ZIF-62 were identified as the main phases and a phasediagram relating the batch composition and the finalproduct was constructed based on XRPD and SEM. Therange of batch composition giving rise to ZIF-7 and ZIF-62was identified from the phase diagram. Changes of crystalsize and morphology of ZIF-7 and ZIF-62 in terms of batchcomposition and synthesis temperature were studied bySEM and different trends were observed for the two ZIFs.Thermogravimetric analysis (TGA) and in situ XRPDshowed that ZIF-62 possesses a similar high thermal stabilityas ZIF-7.
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| 10. |
- Gustafsson, Mikaela, 1980-
(author)
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Metal-Organic Frameworks (MOFs) for Heterogeneous Catalysis : Synthesis and Characterization
- 2012
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Doctoral thesis (other academic/artistic)abstract
- Metal-organic frameworks (MOFs) are crystalline hybrid materials with interesting chemical and physical properties. This thesis is focused on the synthesis and characterization of different MOFs and their use in heterogeneous catalysis.Zeolitic imidazolate frameworks (ZIFs), including ZIF-4, ZIF -7 and ZIF -62, Ln(btc)(H2O) (Ln: Nd, Sm, Eu, Gd, Tb, Ho, Er and Yb), Ln2(bpydc)3(H2O)3, (Ln: Sm, Gd, Nd, Eu, Tb, Ho and Er), MOF-253-Ru and Zn(Co-salophen) MOFs were synthesized. Various characterization techniques were applied to study the properties of these MOFs. X-ray powder diffraction (XRPD), single crystal X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) were extensively used.The effect of synthesis parameters, such as batch composition and temperature, on the formation and morphology of ZIF-7 and ZIF-62 was studied. Structural transformation and flexibility of two series of lanthanide-based MOFs, Ln(btc)(H2O) (Ln: Nd, Ho and Er) and Ln2(bpydc)3(H2O)3, (Ln: Sm and Gd) upon drying and heating were characterized. Relations between metal coordination, structure flexibility and thermal stability among the Sm2(bpydc)3(H2O)3, Nd(btc)(H2O) and MOF-253 were investigated.Salophen- and phenanthroline-based organic linkers were designed, synthesized and characterized. Metal complexes were coordinated to these linkers to be used as catalytic sites within the MOFs.Catalytic studies using two MOF materials, Ln(btc) and MOF-253-Ru, as heterogeneous catalysts in organic transformation reactions were performed. The heterogeneous nature and recyclability of these MOFs were investigated and described.
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