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Alexandra M. Z. Slawin

Bio: Alexandra M. Z. Slawin is an academic researcher from University of St Andrews. The author has contributed to research in topics: Crystal structure & Ligand. The author has an hindex of 85, co-authored 1607 publications receiving 38583 citations. Previous affiliations of Alexandra M. Z. Slawin include International Centre of Insect Physiology and Ecology & University College London.


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TL;DR: It is demonstrated that covalently bonded organic cages can assemble into crystalline microporous materials and design principles for responsive porous organic solids and for the modular construction of extended materials from prefabricated molecular pores are suggested.
Abstract: Porous materials are important in a wide range of applications including molecular separations and catalysis. We demonstrate that covalently bonded organic cages can assemble into crystalline microporous materials. The porosity is prefabricated and intrinsic to the molecular cage structure, as opposed to being formed by non-covalent self-assembly of non-porous sub-units. The three-dimensional connectivity between the cage windows is controlled by varying the chemical functionality such that either non-porous or permanently porous assemblies can be produced. Surface areas and gas uptakes for the latter exceed comparable molecular solids. One of the cages can be converted by recrystallization to produce either porous or non-porous polymorphs with apparent Brunauer–Emmett–Teller surface areas of 550 and 23 m2 g-1, respectively. These results suggest design principles for responsive porous organic solids and for the modular construction of extended materials from prefabricated molecular pores.

857 citations

Journal ArticleDOI
TL;DR: A strategy to overcome the challenge in preparing MOFs from natural products using g-cyclodextrin (g-CD), a symmetrical cyclic oligosaccharide that is mass-produced enzymatically from starch and comprised of eight asymmetric a-1,4-linked dglucopyranosyl residues, and the key to this success lies in the symmetric arrangement within the g-CD torus.
Abstract: Metal–organic frameworks (MOFs) represent an extensive class of porous crystals in which organic struts link metalcontaining clusters. The success in controlling the functionality and structure of MOFs has led to numerous applications, most notably gas adsorption, storage of clean gas fuels, catalysis, separations, and drug delivery. However, the vast majority of MOFs described to date are composed of organic struts derived from non-renewable petrochemical feedstocks and transition metals. The challenge in preparing MOFs from natural products lies in the inherent asymmetry of the building units, which are not amenable to crystallization in the form of highly porous frameworks. Herein, we report a strategy to overcome this problem using g-cyclodextrin (g-CD), a symmetrical cyclic oligosaccharide that is mass-produced enzymatically from starch and comprised of eight asymmetric a-1,4-linked dglucopyranosyl residues. These g-CD building units are then linked by potassium ions, in aqueous media at ambient temperature and pressure, to form a body-centered cubic structure, termed CD-MOF-1, which has the empirical formula [(C48H80O40)(KOH)2]n. CD-MOFs can be prepared entirely from edible ingredients: combining food-grade g-CD with salt substitute (KCl) or potassium benzoate (food additive E212) in bottled water and Everclear grain spirit (EtOH) yields porous frameworks which constitute edible MOFs. While there have been a few reports of MOFs assembled from amino acids, nucleobases, peptides, magnesium formates, and metal glutarates, examples of these materials are not common despite the rapidly growing desire to fabricate MOFs from naturally available building blocks. We suspect that the key to our success in assembling CD-MOFs lies in the symmetric arrangement (C8) within the g-CD torus of eight asymmetric (C1) a-1,4-linked d-glucopyranosyl residues and the ready availability of g-CD as a chiral molecular building block (Figure 1). CD-MOF-1 was prepared by combining 1.0 equiv of g-CD with 8.0 equiv of KOH in aqueous solution, followed by vapor diffusion of MeOH into the solution during 2–7 days, resulting in colorless, cubic, single crystals, suitable for X-ray crystallography, in approximately 70% yield. Other CD-MOFs were readily obtained using salts of Na, Rb, and Cs, giving rise to an extensive new family of porous materials. A complete list of metal salts employed to form CD-MOFs and the full synthesis of CDMOFs are provided in Section S2 of the Supporting Information. The X-ray crystal structure of CD-MOF-1 reveals that eight-coordinate K ions not only assist in the assembly of (gCD)6 cubes (Figure 2a,b), wherein six g-CD units occupy the faces of a cube, but they also serve to link these cubes together in a three-dimensional array which extends throughout the crystal (Figure 2c). The (g-CD)6 repeating motifs adopt a body-centered cubic packing arrangement wherein each symmetrically equivalent K ion links two contiguous g-CD

505 citations

Journal ArticleDOI
TL;DR: An unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system is reported.
Abstract: Linear α-olefins, such as 1-hexene and 1-octene, are important comonomers in the production of linear low-density polyethylene (LLDPE). The conventional method of producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear α-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system.

444 citations


Cited by
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[...]

08 Dec 2001-BMJ
TL;DR: There is, I think, something ethereal about i —the square root of minus one, which seems an odd beast at that time—an intruder hovering on the edge of reality.
Abstract: There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality. Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

33,785 citations

Journal ArticleDOI
30 Aug 2013-Science
TL;DR: Metal-organic frameworks are porous materials that have potential for applications such as gas storage and separation, as well as catalysis, and methods are being developed for making nanocrystals and supercrystals of MOFs for their incorporation into devices.
Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

10,934 citations

Journal ArticleDOI
01 Apr 1988-Nature
TL;DR: In this paper, a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) is presented.
Abstract: Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

9,929 citations