In situ powder X-ray crystallography for gas sorption in metal–organic frameworks

Two mixed-ligand metal–organic frameworks using benzene-1,4-dihydroxamic acid and isonicotinic acid were synthesized and fully characterized by single-crystal X-ray crystallography as well as N2, H2, and CO2 gas-sorption measurements.

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In situ X‐ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)‐based Metal‐Organic Frameworks with UiO‐66 and MIL‐140 architectures

Chemistry - A European Journal ◽

10.1002/chem.202005085 ◽

2021 ◽

Author(s):

Stephen J. I. Shearan ◽

Jannick Jacobsen ◽

Ferdinando Costantino ◽

Roberto D’Amato ◽

Dmitri Novikov ◽

...

Keyword(s):

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic

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Compressibility Studies of Zirconium Based Metal-Organic Frameworks

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314098428 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C157-C157

Author(s):

Claire Hobday ◽

Stephen Moggach ◽

Carole Morrison ◽

Tina Duren ◽

Ross Forgan

Keyword(s):

High Pressure ◽

Mechanical Stability ◽

Metal Organic Frameworks ◽

External Pressure ◽

X Ray Diffraction ◽

X Ray ◽

X Ray Crystallography ◽

Pressure Medium ◽

Metal Organic ◽

University Of Oslo

Metal-organic frameworks (MOFs) are a well-studied class of porous materials with the potential to be used in many applications such as gas storage and catalysis.[1] UiO-67 (UiO = University of Oslo), a MOF built from zirconium oxide units connected with 4,4-biphenyldicarboxylate (BDC) linkers, forms a face centred cubic structure. Zirconium has a high affinity towards oxygen ligands making these bridges very strong, resulting in UiO-based MOFs having high chemical and thermal stability compared to other MOF structures. Moreover, UiO-67 has become popular in engineering studies due to its high mechanical stability.[2] Using high pressure x-ray crystallography we can exert MOFs to GPa pressures, experimentally exploring the mechanical stability of MOFs to external pressure. By immersing the crystal in a hydrostatic medium, pressure is applied evenly to the crystal. On surrounding a porous MOF with a hydrostatic medium composed of small molecules (e.g. methanol), the medium can penetrate the MOF, resulting in medium-dependant compression. On compressing MOF-5 (Zn4O(BDC)3) using diethylformamide as a penetrating medium, the framework was shown to have an increased resistance to compression, becoming amorphous several orders of magnitude higher in pressure than observed on grinding the sample.[3] Here we present a high-pressure x-ray diffraction study on the UiO-based MOF UiO-67, and several new synthesised derivatives built from same metal node but with altered organic linkers, allowing us to study in a systematic way, the mechanical stability of the MOF, and its pressure dependence on both the linker, and pressure medium.

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In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

10.26434/chemrxiv.13252544 ◽

2020 ◽

Author(s):

Stephen Shearan ◽

Jannick Jacobsen ◽

Ferdinando Costantino ◽

Roberto D’Amato ◽

Dmitri Novikov ◽

...

Keyword(s):

Crystal Growth ◽

Metal Organic Frameworks ◽

Building Blocks ◽

Nucleation And Growth ◽

X Ray Diffraction ◽

X Ray ◽

Rate Determining Step ◽

Wide Range ◽

Metal Organic

We report on the results of a thorough in situ synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds in situ in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO3) and amount of the coordination modulator acetic acid (AcOH). When only HNO3 is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO3, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO3 slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO3 favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO3. Based on these in situ results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

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X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

Philosophical Transactions of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rsta.2016.0028 ◽

2017 ◽

Vol 375 (2084) ◽

pp. 20160028 ◽

Cited By ~ 11

Author(s):

Michael T. Huxley ◽

Campbell J. Coghlan ◽

Witold M. Bloch ◽

Alexandre Burgun ◽

Christian J. Doonan ◽

...

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Coordination Sphere ◽

Metal Organic Frameworks ◽

Void Space ◽

X Ray ◽

X Ray Crystallography ◽

Metal Nitrates ◽

Metal Organic

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

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Interpenetrated Double Pillared-Layer CoII MOFs with pcu Topology

Australian Journal of Chemistry ◽

10.1071/ch16438 ◽

2017 ◽

Vol 70 (5) ◽

pp. 461 ◽

Cited By ~ 3

Author(s):

In-Hyeok Park ◽

Yunji Kang ◽

Eunji Lee ◽

Anjana Chanthapally ◽

Shim Sung Lee ◽

...

Keyword(s):

Conformational Changes ◽

Layer Structure ◽

Metal Organic Frameworks ◽

Trans Conformation ◽

X Ray ◽

Pore Sizes ◽

X Ray Crystallography ◽

Metal Organic

Three double pillared-layer CoII metal–organic frameworks (MOFs) with a pcu topology of a long, conformationally flexible, dipyridyl spacer ligand, 1,4-bis[2-(4-pyridyl)ethenyl]benzene (bpeb), and aromatic dicarboxylates (1,4-benzenedicarboxylate (bdc), 2,6-naphthalenedicarboxylate (ndc), and biphenyl-4,4′-dicarboxylate (bpdc)) have been synthesised and structurally characterised by X-ray crystallography. The MOFs are denoted as [Co2(bpeb)2(bdc)2]·DMF·3H2O (1), [Co2(bpeb)2(ndc)2]·1.75DMF·3.75H2O (2), and [Co2(bpeb)2(bpdc)2]·3.5DMF·4H2O (3). In the dinuclear repeating unit, four carboxylates are bonded to two CoII atoms forming a (4,4) layer structure. The axial positions are occupied by bpeb ligands. Of these, 1 and 2 have 2-fold interpenetration, whereas 3 displays 3-fold interpenetration. The two bpeb space ligands in 1 have trans,trans,trans and trans,cis,trans conformations. In contrast, the bpeb ligands in 2 and 3 have a trans,cis,trans conformation. Although the olefin groups in two adjacent bpeb ligands, as the double pillars in 2 and 3, satisfy the conditions for photo-dimerisation to occur, they are photo-inactive. The conformational changes of bpeb, bonding modes of the dicarboxylates, and pore sizes in these double pillared-layer compounds have been discussed.

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In Situ X-ray Absorption Spectroscopy Studies of Kinetic Interaction between Platinum(II) Ions and UiO-66 Series Metal–Organic Frameworks

The Journal of Physical Chemistry B ◽

10.1021/jp5066456 ◽

2014 ◽

Vol 118 (49) ◽

pp. 14168-14176 ◽

Cited By ~ 16

Author(s):

Chaoxian Xiao ◽

Tian Wei Goh ◽

Kyle Brashler ◽

Yuchen Pei ◽

Zhiyong Guo ◽

...

Keyword(s):

Absorption Spectroscopy ◽

Metal Organic Frameworks ◽

X Ray ◽

Metal Organic ◽

Kinetic Interaction ◽

Spectroscopy Studies ◽

X Ray Absorption

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Crystallographic studies of gas sorption in metal–organic frameworks

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520614009834 ◽

2014 ◽

Vol 70 (3) ◽

pp. 404-422 ◽

Cited By ~ 72

Author(s):

Elliot J. Carrington ◽

Iñigo J. Vitórica-Yrezábal ◽

Lee Brammer

Keyword(s):

Energy Transport ◽

Modular Design ◽

Metal Organic Frameworks ◽

X Rays ◽

Gas Sorption ◽

Sorption Behaviour ◽

Crystalline Materials ◽

Metal Organic ◽

Gas Molecules

Metal–organic frameworks (MOFs) are a class of porous crystalline materials of modular design. One of the primary applications of these materials is in the adsorption and separation of gases, with potential benefits to the energy, transport and medical sectors.In situcrystallography of MOFs under gas atmospheres has enabled the behaviour of the frameworks under gas loading to be investigated and has established the precise location of adsorbed gas molecules in a significant number of MOFs. This article reviews progress in such crystallographic studies, which has taken place over the past decade, but has its origins in earlier studies of zeolites, clathratesetc. The review considers studies by single-crystal or powder diffraction using either X-rays or neutrons. Features of MOFs that strongly affect gas sorption behaviour are discussed in the context ofin situcrystallographic studies, specifically framework flexibility, and the presence of (organic) functional groups and unsaturated (open) metal sites within pores that can form specific interactions with gas molecules.

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In situ X-ray absorption spectroscopy data during formation of active Pt- and Pd-sites in functionalized UiO-67 metal-organic frameworks

Data in Brief ◽

10.1016/j.dib.2019.104280 ◽

2019 ◽

Vol 25 ◽

pp. 104280 ◽

Cited By ~ 2

Author(s):

Aram L. Bugaev ◽

Alina A. Skorynina ◽

Elizaveta G. Kamyshova ◽

Kirill A. Lomachenko ◽

Alexander A. Guda ◽

...

Keyword(s):

Absorption Spectroscopy ◽

Metal Organic Frameworks ◽

Spectroscopy Data ◽

X Ray ◽

Metal Organic ◽

X Ray Absorption

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Two topologically different 3D CuII metal–organic frameworks assembled from the same ligands: control of reaction conditions

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520619013209 ◽

2019 ◽

Vol 75 (6) ◽

pp. 1060-1068 ◽

Cited By ~ 1

Author(s):

Shunlin Zhang ◽

Sheng Gao ◽

Xin Wang ◽

Xin He ◽

Jing Zhao ◽

...

Keyword(s):

Thermogravimetric Analysis ◽

Metal Organic Frameworks ◽

High Water ◽

High Dimensional ◽

X Ray Diffraction ◽

Reaction Conditions ◽

X Ray ◽

X Ray Crystallography ◽

Bifunctional Ligands ◽

Metal Organic

Bifunctional ligands containing both carboxylic and sulfonate groups can adopt versatile coordination modes to produce novel metal–organic frameworks (MOFs) with high-dimensional networks and interesting topologies. Using 2,2′-disulfonylbiphenyl-4,4′-dicarboxylic acid (H4 L) as a linker and 4,4′-bipyridine (4,4′-bpy) as a co-ligand, two novel 3D CuII MOFs, {[Cu2(L)(4,4′-bpy)2.5(H2O)]·1.7H2O} n , (1), and {[Cu2(L)(4,4′-bpy)2]·DMA·3H2O} n , (2), have been synthesized and structurally characterized by X-ray crystallography (DMA is N,N-dimethylacetamide). MOF (1) shows an unprecedented trinodal 4,4,5-connected topology network with the Schläfli symbol (4.62.73)(43.65.7.8)(6.73.8.10), while MOF (2) indicates a binodal 4,6-connected fsc network with the Schläfli symbol (44.610.8)(44.62). MOFs (1) and (2) were further characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and thermogravimetric analysis. MOF (1) shows a high water and chemical stability. The proton conductivity of (1) and CO2 adsorption of (2) were also investigated.

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