Novel copper materials based on the self-assembly of organophosphonic acids and bidentate amines

Clarke, Rachael; Latham, Kay; Rix, Colin; Hobday, Malcolm; White, Jonathan M.

doi:10.1039/b416208k

Cited by 37 publications

(23 citation statements)

References 25 publications

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“…However, the geometry of compound 1B is distorted. The equatorial plane is formed by a chlorido liwww.eurjic.org [44,47,51,61,62] Complex 1D displays a Cu-N3 distance of 2.19 Å, which is 0.07 Å longer than the average experimental values. The axial Cu-N lengths of the copper I complex 1B are very long, namely 2.25 Å for Cu-N1, and 2.42 Å for Cu-N3.…”

Section: Calculated Structures Of Complexes 1-7mentioning

confidence: 95%

Influence of the Copper Coordination Geometry on the DNA Cleavage Activity of Clip‐Phen Complexes Studied by DFT

et al. 2008

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Six different Cu(Clip‐Phen)2+/+ complexes, with or without a coordinating chloride ligand, have been investigated by DFT calculations to evaluate the influence of the length and functional substituents of the bridge linking the two phenanthroline units on the DNA cleavage activity. The changes of the structural and energetic profiles imposed by the bridge of these complexes have been analyzed by comparison with the well studied nuclease active agent Cu(phen)22+/+. The present studies show that the bridge length of these complexes is critical for the consequent geometry, and both the strain and ligand binding energies. Upon reduction (needed for the DNA cleavage activity), the geometry of Cu(phen)2 changes drastically. The behavior of the complexes with a 4‐ or 5‐carbon bridge resembles the behavior of Cu(phen)22+/+. However, the geometries of the complexes with two‐ or three‐carbon bridges are markedly different from the one of unbridged Cu(phen)2+, as a result of constraints enforced by the short bridge. The results suggest that the cleaving activities of these bis‐phenanthroline complexes are influenced by the different ligand environment geometries imposed by the bridge, and not by the change of the redox properties. It appears that the influence of the different bridges on the redox properties of the complexes is minor.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Calculated Structures Of Complexes 1-7mentioning

confidence: 95%

Influence of the Copper Coordination Geometry on the DNA Cleavage Activity of Clip‐Phen Complexes Studied by DFT

et al. 2008

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“…6a), but the direction of the shi well ts the results of our measurements and the literature data. 35 We have also considered a few congurations with single pyridinic nitrogen species to stabilize a Cu atom (Fig. S5 †).…”

Section: 1213mentioning

confidence: 99%

Copper on carbon materials: stabilization by nitrogen doping

et al. 2017

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The applicability of Cu/C catalysts is limited by sintering of Cu leading to deactivation in catalytic reactions.We show that the problem of sintering could be resolved by N-doping of the carbon support. Cu nanocatalysts with 1 at% of metal were synthesized by Cu acetate decomposition on N-free and Ndoped (5.7 at% N) mesoporous carbon supports as well as on thermally expanded graphite oxide.Catalytic properties of these samples were compared in hydrogen production from formic acid decomposition. The N-doping leads to a strong interaction of the Cu species with the support providing stabilization of Cu in the form of clusters of less than 5 nm in size and single Cu atoms, which were observed in a significant ratio by atomic resolution HAADF/STEM even after testing the catalyst under harsh conditions of the reaction at 600 K. The mean size of the obtained Cu clusters was by a factor of 7 smaller than that of the particles in the N-free catalyst. The N-doped Cu catalyst possessed good stability in the formic acid decomposition at 478 K for at least 7 h on-stream and a significantly higher catalytic activity than the N-free Cu catalysts. The nature of the strongly interacting Cu species was studied by XPS, XRD and other methods as well as by DFT calculations. The presence of single Cu atoms in the N-doped catalysts should be attributed to their strong coordination by pyridinic nitrogen atoms at the edge of the graphene sheets of the support. We believe that the N-doping of the carbon support will allow expanding the use of Cu/C materials for different applications avoiding sintering and deactivation.

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“…The sheets alternate along the crystallographic b axis with layers consisting of tetrabutylammonium cations to form a lamellar structure. Analogous structures are known for salts with a 2:1 stoichiometry between a bulky organic monocation and phenylphosphonic acid (see Clarke et al, 2005, Latham et al, 2007and Latham et al, 2008, but to our knowledge, this is the first time it has been reported for phenylarsonic acid.…”

Section: Lukas Reck and Wolfgang Schmitt Commentmentioning

confidence: 67%

“…For similar structures containing bulky hydrophobic cations and hydrogen-bonded chains of hydrogen(arylphosphonate)/ arylphosphonic acid, see: Clarke et al (2005); Latham et al (2007Latham et al ( , 2008. For hybrid organic-inorganic polyoxidometalate frameworks including arylarsonic acid ligands, see: Breen, Clé rac et al (2012) ;; ; Onet et al (2011); Breen & Schmitt (2008 Table 1 Selected bond lengths (Å ).…”

Section: Related Literaturementioning

confidence: 99%