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Browsing Journal Articles by Author "Abrahams, BF"
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- ItemCopper(II) coordination polymers of imdc− (H2imdc+ = the 1,3-bis(carboxymethyl)imidazolium cation): unusual sheet interpenetration and an unexpected single crystal-to-single crystal transformation(Royal Society of Chemistry, 2013-10-08) Abrahams, BF; Maynard-Casely, HE; Robson, R; White, KFThe monoanion of 1,3-bis(carboxymethyl)imidazolium (H2imdc+) combines with Cu(II) to produce an undulating 2D coordination polymer of composition [Cu2(imdc)2(CH3OH)2](BF4)2·(CH3OH)(H2O) (1) in which copper acetate-like dimers, linked by imdc− ligands, act as 4-connecting centres. Cationic sheets stack on top of each other in an A, B, A, B… fashion and produce a structure that contains channels running parallel to the plane of network. Tetrafluoroborate anions are located in channels between sheets. Upon removal of coordinated and noncoordinated solvent molecules a single crystal-to-single crystal transformation occurs to yield a similar compound but with BF4 − anions now coordinated. CO2 isotherms measured at 258 and 273 K show only modest uptake of CO2 but provide an indication that the sheets move apart at elevated pressures in order to accommodate the guest molecules. A compound of composition [Cu3(OH)2(imdc)2]·SiF6·2H2O·2MeOH (3), which possesses a 3D network, is formed by the combination of copper(II) acetate, copper(II) hexafluorosilicate and Himdc. In this structure infinite parallel Cu3(OH)2 chains are linked by bridging imdc− ligands to form channels that have an approximately triangular cross-section. These channels are occupied by SiF6 2− anions in addition to solvent molecules. When copper(II) acetate is combined with Himdc in the appropriate ratio, a 1D coordination polymer of composition Cu(imdc)2 (4) is formed in which pairs of imdc− anions bridge Cu(II) centres. When the reaction is performed in the presence of NaBF4 a minor crystalline product with tetragonal symmetry is isolated in addition to the 1D coordination polymer. This compound of composition Cu2(imdc)4NaBF4·7H2O (5) consists of 2D Cu(imdc)2 networks and features an unusual mode of interpenetration. © 2013, The Royal Society of Chemistry.
- ItemThe effect of sterically active ligand substituents on gas adsorption within a family of 3D Zn-based coordination polymers(American Chemical Society, 2020-06-09) Abrahams, BF; Babarao, R; Dharma, AD; Holmes, JL; Hudson, TA; Maynard-Casely, HE; McGain, F; Robson, R; Waite, KFAn investigation of the adsorption properties of two structurally related, 3D coordination polymers of composition Zn(2-Mehba) and Zn(2,6-Me2hba) (2-Mehba = the dianion of 2-methyl-4-hydroxybenzoic acid and 2,6-Me2hba = the dianion of 2,6-dimethyl-4-hydroxybenzoic acid) is presented. A common feature of these structures are parallel channels that are able to accommodate appropriately sized guest molecules. The structures differ with respect to the steric congestion within the channels arising from methyl groups appended to the bridging ligands of the network. The host network, Zn(2-Mehba), is able to take up appreciable quantities of H2 (77 K) and CO2 and CH4 (298 K) in a reversible manner. In regard to the adsorption of N2 by Zn(2-Mehba), there appears to be an unusual temperature dependence for the uptake of the gas such that when the temperature is increased from 77 to 298 K the uptake of N2 increases. The relatively narrow channels of Zn(2,6-Me2hba) are too small to allow the uptake of N2 and CH4, but H2 molecules can be adsorbed. A pronounced step at elevated pressures in CO2 and N2O isotherms for Zn(2,6-Me2hba) is noted. Calculations indicate that rotation of phenolate rings leads to a change in the available intraframework space during CO2 dosing. © 2020 American Chemical Society
- ItemLi+ and Ca2+ derivatives of the isonicotinate-n-oxide ion including single crystal-to-single crystal transformations(Americal Chemical Society, 2014-07-29) White, KF; Abrahams, BF; Maynard-Casely, HE; Robson, RCrystals of [Li(inox)(H2O)] (where inox– = the isonicotinate-N-oxide ion) are obtained from aqueous solution. The Li+ cations and the carboxylate anions form a two-dimensional (2D) sheet containing four-membered (−Li–O–Li–O−) rings and 16-membered (−Li–O–C–O−)4 rings; the sheets are linked to adjacent parallel sheets through hydrogen bonds. Crystals of solvent-free [Li(inox)], obtained from t-butanol, consist of a three-dimensional network which can also be prepared in microcrystalline form by dehydration of [Li(inox)(H2O)] at 200 °C. Crystals of [Ca(inox)2(H2O)2] contain 2D sheets with 4,4 topology in which Ca2+ ions, bound by trans water molecules, provide the 4-connecting nodes. The Ca(H2O)22+ units are linked by carboxylate groups to generate 16-membered (−Ca–O–C–O−)4 rings. Sheets are bound together by hydrogen bonds between the pyridine-N-oxide units and coordinated water molecules. [Ca(inox)2(H2O)2] can be dehydrated at 190 °C in a single crystal-to-single crystal transformation to give [Ca(inox)2] whose structure is related to that of the hydrated precursor. A proposed solid-state mechanism for this single crystal-to-single crystal transformation, in which the N-oxide takes up the site on calcium vacated by water is proposed © 2014 American Chemical Society.
- ItemNew family of ferric spin clusters incorporating redox-active ortho-dioxolene ligands.(American Chemical Society, 2009-08-17) Mulyana, Y; Nafady, A; Mukherjee, A; Bircher, R; Moubaraki, B; Murray, KS; Bond, AM; Abrahams, BF; Boskovic, CSeven new di-, tri-, tetra-, and hexanuclear iron complexes that incorporate a polydentate Schiff base and variously substituted catecholate ligands have been synthesized from the trinuclear precursor [Fe3(OAc)3(L)3] (1), where LH2 = 2-[[(2-hydroxyethyl)imino]phenylmethyl]-phenol. These were isolated as the compounds [Fe3(OAc)(Cat)(L)3] (2), [Fe6(OAc)2(Cat)4(L)4] (3), [Fe4(3,5-DBCat)2(L)4] (4), [Bu4N][Fe4(OAc)(3,5-DBCat)4(L)2] (5a, 5- is the complex monoanion [Fe4(OAc)(3,5-DBCat)4(L)2]-), [Fe4(OAc)(3,5-DBCat)3(3,5-DBSQ)(L)2] (6), [Fe2(Cl4Cat)2(L)(LH2)(H2O)] (7), and [Et3NH]2[Fe2(Cl4Cat)2(L)2] (8a, 8²- is the complex dianion [Fe2(Cl4Cat)2(L)2]2-), where CatH2 = catechol; 3,5- DBCatH2 = 3,5-di-tert-butyl-catechol; 3,5-DBSQH = 3,5-di-tert-butyl-semiquinone, and Cl4CatH2 = tetrachlorocatechol. While compounds 2-4, 5a, 7, and 8a were obtained by directly treating 1 with the appropriate catechol, compound 6 was synthesized by chemical oxidation of 5a. These compounds have been characterized by single crystal X-ray diffraction, infrared and UV-visible spectroscopy, voltammetry, UV-visible spectroelectrochemistry, andmagnetic susceptibility and magnetization measurements. An electrochemical study of the three tetranuclear complexes (4, 5-, and 6) reveals multiple reversible redox processes due to the o-dioxolene ligands, in addition to reductive processes corresponding to the reduction of the iron(III) centers to iron(II). A voltammetric study of the progress of the chemical oxidation of compound 5a, together with a spectroelectrochemical study of the analogous electrochemical oxidation, indicates that there are two isomeric forms of the one-electron oxidized product. A relatively short-lived neutral species (5) that possesses the same ligand arrangement as complex 5- is the kinetic product of both chemical and electrochemical oxidation. After several hours, this species undergoes a significant structural rearrangement to convert to complex 6, which appears to be largely driven by the preference for the 3,5-DBSQ- ligand to bind in a non-bridging mode. Variable temperature magnetic susceptibilitymeasurements for compounds 3, 4, 5a, 6, 7, and8a reveal behavior dominated by pairwise antiferromagnetic exchange interactions, giving rise to a poorly isolated S = 0 ground state spin for compound 3, well-isolated S = 0 ground state spins for complexes 4, 5-, 7 and 8²-, and a well-isolated S = 1/2 ground state spin for complex 6. The ground state spin values were confirmed by low temperature variable field magnetization measurements. The thermal variation of the magnetic susceptibility for compounds 3, 4, 5a, 6, 7, and 8a were fitted and/or simulated using the appropriate Hamiltonians to derive J values that are consistent with magnetostructural correlations that have been reported previously for alkoxobridged ferric complexes. © 2009, American Chemical Society
- ItemSquare grid metal–chloranilate networks as robust host systems for guest sorption(John Wiley & Sons, Inc, 2019-02-02) Kingsbury, CJ; Abrahams, BF; Auckett, JE; Chevreau, H; Dharma, AD; Duyker, SG; He, QL; Hua, C; Hudson, TA; Murray, KS; Phonsri, W; Peterson, VK; Robson, R; White, KFReaction of the chloranilate dianion with Y(NO3)3 in the presence of Et4N+ in the appropriate proportions results in the formation of (Et4N)[Y(can)2], which consists of anionic square-grid coordination polymer sheets with interleaved layers of counter-cations. These counter-cations, which serve as squat pillars between [Y(can)2] sheets, lead to alignment of the square grid sheets and the subsequent generation of square channels running perpendicular to the sheets. The crystals are found to be porous and retain crystallinity following cycles of adsorption and desorption. This compound exhibits a high affinity for volatile guest molecules, which could be identified within the framework by crystallographic methods. In situ neutron powder diffraction indicates a size-shape complementarity leading to a strong interaction between host and guest for CO2 and CH4. Single-crystal X-ray diffraction experiments indicate significant interactions between the host framework and discrete I2 or Br2 molecules. A series of isostructural compounds (cat)[MIII(X-an)2] with M=Sc, Gd, Tb, Dy, Ho, Er, Yb, Lu, Bi or In, cat=Et4N, Me4N and X-an=chloranilate, bromanilate or cyanochloranilate bridging ligands have been generated. The magnetic properties of representative examples (Et4N)[Gd(can)2] and (Et4N)[Dy(can)2] are reported with normal DC susceptibility but unusual AC susceptibility data noted for (Et4N)[Gd(can)2]. © 2019 Wiley-VCH Verlag GmbH & Co
- ItemSynthesis, structure and magnetic properties of a novel Tb4 spin cluster and synthesis of a Tb chain(Elsevier, 2007-08-06) Bircher, R; Abrahams, BF; Gudel, HU; Boskovic, CThe syntheses of two new polynuclear TbIII compounds are reported. A tetranuclear complex [Tb4(H2L)2(H4L)2(OAc)8] (1), with H4L=2-((2-hydroxy-benzylidene)-amino)-2-hydroxy-methyl-propane-1,3-diol, has a butterfly-type structure, while [Tb(OAc)3MeOH]∞ (2) is a linear chain. A novel binding mode for H2L2− is observed in 1, with two alkoxides each bridging three TbIII ions. The magnetic properties of 1 are determined by the superposition of the ligand field split 7F6 states of TbIII single-ions located on two crystallographically distinct sites. Weak antiferromagnetic exchange interactions possibly contribute to the lowering of the magnetic moment at the lowest temperatures. © 2007, Elsevier Ltd.