Copper(II) complexes of the isomeric tetraazamacrocyclic ligands 1,11- and 1,8-bis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane and of the 1,4,8,11-tetraazacyclotetradecane-5,12-dione analogue at neutral and basic pH

Goeta, Andrés E.; Howard, Judith A. K.; Maffeo, Davide; Puschmann, Horst; Williams, J. A. Gareth; Yufit, Dimitrii S.

doi:10.1039/b000739k

Cited by 48 publications

(49 citation statements)

References 15 publications

(13 reference statements)

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“…methanol does not affect the shape nor the position of the absorption band. The electronic spectrum of cyclam-Cu complex in a square-planar form [71][72][73][74] or distorted-octahedral geometry exhibits a quite broad absorption band between 540 and 600 nm, as it is shown in Fig. 10.…”

Section: Cyclam-copper Moleculesmentioning

confidence: 81%

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Makowska‐Janusik

Kassiba

Errien

et al. 2010

J Inorg Organomet Polym

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Mesoporous silica functionalized by cyclammetal molecules were investigated by spectroscopic methods including Raman, IR, UV-VIS absorption and EPR technique. To analyse quantitatively the physical features, numerical models were developed using the density functional theory method. Thus, the construction of molecular geometries and their optimisation analysis were achieved on the cyclam-metal molecules in vacuum as well as constrained by the host mesoporous silica matrixes. In this context and with regard to the paramagnetic nature of the metals chelated by cyclam molecules, EPR technique allows probing the metal environments which can be compared to theoretical results inferred from numerical models. The vibrational and optical properties were exhaustively investigated and the assignment of the main features was quantitatively discussed thanks to the carried out numerical analyses. The developed approach point out the possibility to define a targeted application of such functional materials based on the possibility to fine tune the absorption features in a wide wavelength range by stabilizing defined configurations of the cyclam-metal groups.

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Section: Cyclam-copper Moleculesmentioning

confidence: 81%

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Makowska‐Janusik

Kassiba

Errien

et al. 2010

J Inorg Organomet Polym

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“…Cyclam [62] constitutes a useful building block for the creation of porous hybrid systems, since it results in a scaffold possessing four polycondensation directions with a central cavity able to coordinate transition-metal ions. The various topologies of the ligands lead to a wide variety of coordination modes with metal centers; examples of these are square-planar, square-pyramidal, [60,[63][64][65][66] and octahedral coordination geometry, and square antiprism polyhedra, [59,[67][68][69] depending on the number and the nature of the coordinating arms anchored to the macrocycle and the stereochemical constraints. The incorporation of tetraazamacrocycles in a material should yield stabilization of unusual metal coordination stereochemistries and reactivity of the complexes.…”

Section: -Peroxodicopper(ii) and Bisa C H T U N G T R E N N U N G (M-mentioning

confidence: 99%

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Brandès

David

Suspène

et al. 2007

Chemistry A European J

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We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2) adsorption; this is induced by close confinement of the two copper ions leading to end-on mu-eta(1):eta(1)-peroxodicopper(II) complexes. The anisotropic packing of the tetraazamacrocycle in a lamellar structure induces an exceptional reactivity of these copper complexes. We show for the first time that the organic-inorganic environment of copper complexes in a silica matrix fully model the protecting role of protein in metalloenzymes. For the first time an oxygenated dicopper(II) complex can be isolated in a stable form at room temperature, and the reduced Cu(2) (I,I) species can be regenerated after several adsorption-desorption cycles. These data also demonstrate that the coordination scheme and reactivity of the copper cyclams within the solid are quite different from that observed in solution.

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“…[12][13][14] On the other hand, L 9 forms a five-coordinate complex in which one of the pyridyl groups is not involved in the coordination. 15 It has been also reported that L 2 reacts with Cu 2+ ion more slowly than does the unsubstituted macrocycle L 1 . 12 This observation contradicts those reported for other 14-membered tetraaza macrocycles bearing two or four 2-hydroxyethyl pendant arms.…”

Section: -15mentioning

confidence: 96%

“…Although L 2 , L 8 , and L 9 bearing two N-(2-pyridylmethyl) groups typically form mononuclear complexes, the fully N-substituted macrocycle L 7 acts as a binucleating ligand. 8,9,[12][13][14][15] The two pyridyl groups in [CuL 2 ] 2+ or [CuL 8 ] 2+ are coordinated to the metal ion. [12][13][14] On the other hand, L 9 forms a five-coordinate complex in which one of the pyridyl groups is not involved in the coordination.…”

Section: -15mentioning

confidence: 99%

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Synthesis and Properties of Tetraaza Macrocycles Containing Two 3-Pyridylmethyl, 4-Pyridylmethyl, or Phenylmethyl Pendant Arms and Their Nickel(Ⅱ) and Copper(Ⅱ) Complexes: Effects of the Pendant Arms on the Complex Formation Reaction

2003

Bulletin of the Korean Chemical Society

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The synthesis and properties of 2,13-bis(3'-pyridylmethyl) (L 3 ), 2,13-bis(4'-pyridylmethyl) (L 4 ), and 2,13-bis(phenylmethyl) (L 5 ) derivatives of 5, 16-dimethyl-2,6,13,17-tetraazatrcyclo[16.4.0. and L 4 react with copper(II) ion more rapidly than does L 5 at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3-or 4-pyridylmethyl pendant arms on the complex formation reaction of L 3 and L 4 are discussed.

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Copper(II) complexes of the isomeric tetraazamacrocyclic ligands 1,11- and 1,8-bis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane and of the 1,4,8,11-tetraazacyclotetradecane-5,12-dione analogue at neutral and basic pH

Abstract: Copper(II) complexes of the isomeric tetraazamacrocyclic ligands 1,11-and 1,8-bis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane and of the 1,4,8,11-tetraazacyclotetradecane-5,12-dione analogue at neutral and basic pH

Cited by 48 publications

References 15 publications

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Mesoporous Silica Functionalized by Cyclam–Metal Groups: Spectroscopic Studies and Numerical Modeling

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Synthesis and Properties of Tetraaza Macrocycles Containing Two 3-Pyridylmethyl, 4-Pyridylmethyl, or Phenylmethyl Pendant Arms and Their Nickel(Ⅱ) and Copper(Ⅱ) Complexes: Effects of the Pendant Arms on the Complex Formation Reaction

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