0000000001309784
AUTHOR
Paul E. Kruger
Metamorphosis of a butterfly: synthesis, structural, thermal, magnetic and DFT characterisation of a ferromagnetically coupled tetranuclear copper(ii) complex
The reaction in water of Cu(OH)(2) with 2,2'-bipyridine (bipy) and (NH(4))(2)HPO(4) in a 4 : 4 : 2 molar ratio under an inert atmosphere leads to the formation of a tetranuclear copper(II) complex of formula {[(H(2)O)(2)Cu(4)(bipy)(4)(mu(4)-PO(4))(2)(mu(2)-OH)] x 0.5 HPO(4) x 15.5 H(2)O}, 1, with butterfly topology. The structure of the tetranuclear core in 1 consists of four crystallographically unique copper(II) ions in approximate square-pyramidal geometry with each coordinated to a bipy ligand and interacting through two mu(4)-O,O',O''-phosphate bridges. Additional bridging between Cu(3) and Cu(4) is provided by a hydroxide ligand, whereas two water molecules cap the Cu(1) and Cu(2) squ…
Synthesis, Structural, Thermal and Magnetic Characterization of a Pyrophosphato‐Bridged Cobalt(II) Complex
The reaction in water of CoII sulfate heptahydrate with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na4P2O7) in a 2:4:1 stoichiometric ratio resulted in the crystallization of a neutral dinuclear CoII complex, {[Co(phen)2]2(μ-P2O7)}·6MeOH (1), as revealed by a single-crystal X-ray diffraction study. The bridging pyrophosphato ligand between the two [Co(phen)2]2+ units in a bis(bidentate) coordination mode places the adjacent metal centers at 4.857 A distance, and its conformation gives rise to intramolecular π–π stacking interaction between adjacent phen ligands. Indeed, intermolecular π–π stacking interactions between phen ligands from adjacent dinuclear complexes create a supramo…
Synthesis, X‐ray Crystal Structure and Magnetic Properties of Oxalato‐Bridged Copper( II ) Complexes with 2,3‐Bis(2‐pyridyl)pyrazine, 2,3‐Bis(2‐pyridyl)quinoxaline and 2,2′‐Bipyrazine as Peripheral Ligands
Five oxalate-containing copper(II) complexes of formula [Cu(dpq)(H2O)(ox)]·5H2O (1), [Cu(dpp)(H2O)(ox)]·H2O (2), [Cu(bpz)(ox)]n (3), [Cu2(dpp)2(H2O)2(NO3)2(ox)]·4H2O (4) and [Cu2Cl2(bpz)2(H2O)2(ox)][Cu(bpz)(H2O)2(ox)]·2H2O (5) [dpq = 2,3-bis(2-pyridyl)quinoxaline; dpp = 2,3-bis(2-pyridyl)pyrazine; bpz = 2,2′-bipyrazine; ox = oxalate] were prepared and their structures were determined by X-ray diffraction on single crystals. Complexes 1 and 2 are discrete mononuclear complexes with oxalate and dpq (1)/dpp (2) acting as bidentate ligands. Complex 3 is a neutral oxalato-bridged (2,2′-bipyrazine)copper(II) chain where the oxalate adopts a bidentate/monodentate coordination mode, whereas 4 is an…
Syntheses, crystal structures and magnetic properties of copper(II) polynuclear and dinuclear compounds with 2,3-bis(2-pyridyl)pyrazine (dpp) and pseudohalide as ligands
Abstract The preparation, crystal structures and magnetic properties of four heteroleptic copper(II) complexes with 2,3-bis(2-pyridyl)pyrazine (dpp) and azide, cyanate or thiocyanate as ligands are reported, [Cu(dpp)(N3)2]n (1), [Cu(dpp)(NCO)2]n (2), [Cu(dpp)(NCS)2]2 (3) and [Cu(H2O)(dpp)(NCS)2]2·2H2O (4). Compounds 1 and 2 are isomorphous, triclinic, space group P1, and consist of mononuclear building blocks featuring copper atoms with close to square planar coordination geometries. The mononuclear units are, however, associated into chains through weak axial Cu–N bonds formed by end-on asymmetrically bridging azido/cyanato groups and by pyridyl nitrogen atoms. Taking these contacts into a…
Coordination complexes incorporating pyrophosphate: Structural overview and exploration of their diverse magnetic, catalytic and biological properties
Abstract Current attention continues to revolve around the chemistry and biochemistry associated with polyphosphate anions because of their importance in biology. A pivotal intermediate within this family is the pyrophosphate tetraanion, P2O74−. Considering its biological relevance and the multidentate nature that makes it an ideal ligand in the field of the coordination chemistry, there is a growing interest in the use of this anion in building new class of molecules/compounds for different purposes. While the total number of characterized structures still remains modest, several new pyrophosphate-containing coordination complexes have been reported in the last decade, as well as different…
A dihydrogen arsenate-mediated supramolecular network: crystal structure and magnetic properties of {[(bipy)Cu(μ-H2AsO4)(H2AsO4)]2}n
Treatment of an aqueous suspension of Cu(OH)2 and 2,2′-bipyridine (bipy) with either Na2HAsO4·7H2O (1∶1∶2) or As2O5 (1∶1∶1) yields single crystals of {[(bipy)Cu(μ-H2AsO4)(H2AsO4)]2}n, 1, on standing. The solid-state structure of 1 consists of a three dimensional supramolecular network, supported by a combination of coordination covalent, hydrogen bonding and face-to-face π–π interactions. Variable temperature magnetic susceptibility measurements reveal very weak antiferromagnetic coupling between Cu(II) centres across the dihydrogen arsenate bridges (J = −0.58 cm−1).
Self-assembly of M4L4 tetrahedral cages incorporating pendant P=S and P=Se functionalised ligands
Herein, the synthesis of metal–organic tetrahedral cages featuring flexible thio- and selenophosphate-based ligands is described. The cages were prepared by sub-component self-assembly of A=P(OC6H4NH2-4)3 (A = S, Se) or S=P(SC6H4NH2-4)3,2-pyridinecarboxaldehyde, and either Fe[BF4]2 or Co[BF4]2. Preliminary host–guest studies into the ability of the pendant PQS and PQSe groups to interact with suitable substrates will be discussed. peerReviewed
Self-assembly of M4L4tetrahedral cages incorporating pendant PS and PSe functionalised ligands
Herein, the synthesis of metal–organic tetrahedral cages featuring flexible thio- and selenophosphate-based ligands is described. The cages were prepared by sub-component self-assembly of AP(OC6H4NH2-4)3 (A = S, Se) or SP(SC6H4NH2-4)3, 2-pyridinecarboxaldehyde, and either Fe[BF4]2 or Co[BF4]2. Preliminary host–guest studies into the ability of the pendant PS and PSe groups to interact with suitable substrates will be discussed.
Sulfate-Templated 2D Anion-Layered Supramolecular Self-Assemblies
Summary Using solution and solid-state analyses, we demonstrate that the tripodal N-methylated(1,3,5-benzene-tricarboxamide)-tris(phenylurea) BTA ligands, possessing urea functionalities in the meta position, are able to form extended self-assembly 2D networks via hydrogen bonding templated by sulfate (SO42–). The divergence of the urea binding sites confers a propeller-like conformation to the ligands and is key to formation of the self-assemblies. Studies in solution and in the solid state as well as scanning electron microscopy (SEM) on the self-assembly properties of the ligands showed that the convergence also leads to the formation of hierarchical structures, including porous films an…
Hydrogen-bond tuning of ferromagnetic interactions: synthesis, structure and magnetic properties of polynuclear copper(ii) complexes incorporating p-block oxo-anions
The reaction of copper(II) hydroxide with 2,2'-bipyridine (bipy) (1 : 1) in alkaline aqueous solution (pH 14) at room temperature affords the alternating carbonate/hydroxo-bridged copper(II) polymeric chain compound {[Cu3(bipy)3(mu-OH)2(mu-CO3)2].11H2O}n, 1, as determined by single-crystal X-ray diffraction. The structure of 1 is built up from two similar centro-symmetric dinuclear [(bipy)Cu(mu-OH)]2 cores which link together via bridging carbonate groups to mononuclear [(bipy)Cu] fragments to form the chain. Interdigitation of adjacent chains through pi-pi interactions, which involve each bipy ligand, forms sheets that are separated by the water molecules of crystallisation. Variable-tempe…
CCDC 1874341: Experimental Crystal Structure Determination
Related Article: Anna B. Aletti, Salvador Blasco, Savyasachi J. Aramballi, Paul E. Kruger, Thorfinnur Gunnlaugsson|2019|Chem Cell mPress|5|2617|doi:10.1016/j.chempr.2019.06.023
CCDC 1938076: Experimental Crystal Structure Determination
Related Article: Patrick W. V. Butler, Paul E. Kruger, Jas S. Ward|2019|Chem.Commun.|55|10304|doi:10.1039/C9CC05443J
CCDC 1874342: Experimental Crystal Structure Determination
Related Article: Anna B. Aletti, Salvador Blasco, Savyasachi J. Aramballi, Paul E. Kruger, Thorfinnur Gunnlaugsson|2019|Chem Cell mPress|5|2617|doi:10.1016/j.chempr.2019.06.023
CCDC 1874344: Experimental Crystal Structure Determination
Related Article: Anna B. Aletti, Salvador Blasco, Savyasachi J. Aramballi, Paul E. Kruger, Thorfinnur Gunnlaugsson|2019|Chem Cell mPress|5|2617|doi:10.1016/j.chempr.2019.06.023
CCDC 1938073: Experimental Crystal Structure Determination
Related Article: Patrick W. V. Butler, Paul E. Kruger, Jas S. Ward|2019|Chem.Commun.|55|10304|doi:10.1039/C9CC05443J
CCDC 1938074: Experimental Crystal Structure Determination
Related Article: Patrick W. V. Butler, Paul E. Kruger, Jas S. Ward|2019|Chem.Commun.|55|10304|doi:10.1039/C9CC05443J
CCDC 1938075: Experimental Crystal Structure Determination
Related Article: Patrick W. V. Butler, Paul E. Kruger, Jas S. Ward|2019|Chem.Commun.|55|10304|doi:10.1039/C9CC05443J