The structure of Ni(cyclam)(ClO4)2

Prasad, L.; Nyburg, S. C.; McAuley, Alexander

doi:10.1107/s0108270187093090

Cited by 22 publications

(8 citation statements)

References 4 publications

(5 reference statements)

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“…The C−N−C angles are significantly decreased to 111.1° (L 1 ), and 107.9° and 108.0° (L 2 ), giving N−N distances of 2.887 and 2.717 Å (L 1 ), and 2.969, 2.806, and 2.812 Å (L 2 ), considerably shorter than those in the Ni(I) complexes. Again for comparison, the information from the crystal structures of Ni II (L 1 ) and Ni II (L 2 ) is also included in the table. Once again, the gas-phase results resemble the measured crystal structure.…”

Section: Resultsmentioning

confidence: 99%

Solvation Largely Accounts for the Effect of N-Alkylation on the Properties of Nickel(II/I) and Chromium(III/II) Cyclam Complexes

et al. 2002

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The source of the effect of N-alkylation on the redox properties of Ni(II/I) and Cr(III/II) cyclam complexes has been investigated using DFT calculations. The structures of the anhydrous and hydrated complexes were optimized in the gas phase, and single point calculations were performed in a polarized continuum. The main results are the following: the decrease in outer sphere solvation upon N-alkylation is the major source of the relative stabilization of the lower oxidation state complexes by the tertiary amine ligands; tertiary amine nitrogen donors are stronger sigma-donors than the secondary amines, as predicted from the inductive effect of alkyls; steric strain elongates the metal-nitrogen bonds in the tertiary complexes and decreases the ligand strain energies; and the site of water binding to the complexes differs because of their different electronic structures (i.e., in the Ni complexes, the water molecules bind to the M[bond]N[bond]H sites, whereas in the Cr complexes they bind to the central metal cation). Outer sphere hydrogen bonding of water to the ligands in the coordination sphere lowers the ionization potentials by charge delocalization.

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Section: Resultsmentioning

confidence: 99%

Solvation Largely Accounts for the Effect of N-Alkylation on the Properties of Nickel(II/I) and Chromium(III/II) Cyclam Complexes

et al. 2002

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“…The structure is severely disordered, similar to its transperchlorate analogue. 20 The [cis-Ni(cyclam)(BH 4 )] + cation is located on a mirror plane passing through Ni(1), B(1) and B(2) atoms. Because the single cis-Ni(cyclam) moiety is chiral this operation generates two overplayed species with ½ occupancy each.…”

Section: Crystal Structure Of Cis-ni(cyclam)(bh 4 )mentioning

confidence: 99%

Nickel macrocycles with complex hydrides—new avenues for hydrogen storage research

Churchard

Cyrański

Budzianowski

et al. 2010

Energy Environ. Sci.

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“…In fact, the metal center lies only 0.033 Å out of the N 4 mean plane, and the four nitrogen atoms are displaced with respect to the plane with distances ranging from 0.025 to 0.034 Å. The Ni II −N distances, ranging over the 1.933−1.974 Å interval, are those expected for a nickel(II) ion in its low-spin state . The two perchlorate ions are located along the axis perpendicular to the four-nitrogen plane, but the long Ni II −O distances (3.037 and 3.272 Å respectively for the two ions) exclude any serious interaction of ClO 4 - with the metal.…”

Section: Resultsmentioning

confidence: 93%

Water Soluble Molecular Switches of Fluorescence Based on the Ni^III/Ni^IIRedox Change

et al. 2002

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The water soluble Ni(II) complexes of the cyclam derivatives with 1,3-benzodioxole and 1,2,3-trimethoxybenzene display the fluorescent emission typical of the covalently linked fluorophores, which results from a charge transfer excited state. On oxidation to Ni(III), the fluorescence is completely quenched due to the occurrence of an electron transfer (eT) process from the excited fluorogenic fragment Fl to the oxidized metal. Thus, fluorescence can be switched off/on at will, for several cycles, by consecutively oxidizing and reducing the metal center, in controlled potential electrolysis experiments both in acetonitrile and in aqueous 0.1 M HClO4. Occurrence of an eT process from Fl to Ni(III) ultimately depends upon the easy oxidation of Fl to Fl+, whereas failure of the occurrence of an eT process from Ni(II) to Fl has to be ascribed to the particular resistance of Fl fragments to the reduction.

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The structure of Ni(cyclam)(ClO4)2

Cited by 22 publications

References 4 publications

Solvation Largely Accounts for the Effect of N-Alkylation on the Properties of Nickel(II/I) and Chromium(III/II) Cyclam Complexes

Solvation Largely Accounts for the Effect of N-Alkylation on the Properties of Nickel(II/I) and Chromium(III/II) Cyclam Complexes

Nickel macrocycles with complex hydrides—new avenues for hydrogen storage research

Water Soluble Molecular Switches of Fluorescence Based on the Ni^III/Ni^IIRedox Change

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The structure of Ni(cyclam)(ClO4)2

Cited by 22 publications

References 4 publications

Solvation Largely Accounts for the Effect of N-Alkylation on the Properties of Nickel(II/I) and Chromium(III/II) Cyclam Complexes

Solvation Largely Accounts for the Effect of N-Alkylation on the Properties of Nickel(II/I) and Chromium(III/II) Cyclam Complexes

Nickel macrocycles with complex hydrides—new avenues for hydrogen storage research

Water Soluble Molecular Switches of Fluorescence Based on the NiIII/NiIIRedox Change

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Product

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Water Soluble Molecular Switches of Fluorescence Based on the Ni^III/Ni^IIRedox Change