Crystal structure of (perchlorato-κO)(1,4,7,10-tetraazacyclododecane-κ4N)copper(II) perchlorate

Gray, Jessica L.; Gerlach, Deidra L.; Papish, Elizabeth T.

doi:10.1107/s2056989016019563

Cited by 4 publications

(4 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In turn, peaks of Cu 2+ -DO4S, Cu 2+ -DO3S, and Cu 2+ -DO3SAm are red-shifted with respect to that of Cu 2+ -DOT- n -Bu, so that a different coordination mode is suggested when sulfanyl arms replace tert -butyl ones; i.e., one or more sulfur atoms should be involved in the metal binding. Conversely, the visible bands attributed to the d–d transition (above 500 nm) are much more similar for all ligands. ,, The extinction coefficients in the visible region are remarkably high, which can be explained by the so-called intensity-stealing or intensity-borrowing of a neighboring higher-energy transition. A strongly distorted arrangement is thus suggested .…”

Section: Resultsmentioning

confidence: 78%

“…Conversely, the visible bands attributed to the d–d transition (above 500 nm) are much more similar for all ligands. 41 , 49 , 50 The extinction coefficients in the visible region are remarkably high, which can be explained by the so-called intensity-stealing or intensity-borrowing of a neighboring higher-energy transition. A strongly distorted arrangement is thus suggested.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in ^64/67Cu Radiopharmaceuticals

et al. 2021

View full text Add to dashboard Cite

The Cu 2+ complexes formed by a series of cyclen derivatives bearing sulfur pendant arms, 1,4,7,10-tetrakis[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO4S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-1,4,7,10-tetraazacyclododecane (DO3S), 1,4,7-tris[2-(methylsulfanyl)ethyl]-10-acetamido-1,4,7,10-tetraazacyclododecane (DO3SAm), and 1,7-bis[2-(methylsulfanyl)ethyl]-4,10-diacetic acid-1,4,7,10-tetraazacyclododecane (DO2A2S), were studied in aqueous solution at 25 °C from thermodynamic and structural points of view to evaluate their potential as chelators for copper radioisotopes. UV–vis spectrophotometric out-of-cell titrations under strongly acidic conditions, direct in-cell UV–vis titrations, potentiometric measurements at pH >4, and spectrophotometric Ag + –Cu 2+ competition experiments were performed to evaluate the stoichiometry and stability constants of the Cu 2+ complexes. A highly stable 1:1 metal-to-ligand complex (CuL) was found in solution at all pH values for all chelators, and for DO2A2S, protonated species were also detected under acidic conditions. The structures of the Cu 2+ complexes in aqueous solution were investigated by UV–vis and electron paramagnetic resonance (EPR), and the results were supported by relativistic density functional theory (DFT) calculations. Isomers were detected that differed from their coordination modes. Crystals of [Cu(DO4S)(NO 3 )]·NO 3 and [Cu(DO2A2S)] suitable for X-ray diffraction were obtained. Cyclic voltammetry (CV) experiments highlighted the remarkable stability of the copper complexes with reference to dissociation upon reduction from Cu 2+ to Cu + on the CV time scale. The Cu + complexes were generated in situ by electrolysis and examined by NMR spectroscopy. DFT calculations gave further structural insights. These results demonstrate that the investigated sulfur-containing chelators are promising candidates for application in copper-based radiopharmaceuticals. In this connection, the high stability of both Cu 2+ and Cu + complexes can represent a key parameter for avoiding in vivo demetalation after bioinduced reduction to Cu + , often observed for other well-known chelators that can stabilize only Cu 2+ .

show abstract

Section: Resultsmentioning

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in ^64/67Cu Radiopharmaceuticals

et al. 2021

View full text Add to dashboard Cite

show abstract

“…The copper(II) complexes of bipyridine and phenanthroline were prepared by the modified method. [ 35,36 ] To the solution of the ligands, bipyridine, or phenanthroline (1 equiv.) in 30 ml of methanol, copper(II) perchlorate hexahydrate (0.5 equiv.)…”

Section: Experimental Methodsmentioning

confidence: 99%

Copper(II) complex intercalated graphene oxide nanocomposites as versatile, reusable catalysts for click reaction

Samuel

Nagarajan

Cidhuraj

et al. 2020

Applied Organom Chemis

View full text Add to dashboard Cite

In this work, we report the efficient, high stable copper(II) complexes intercalated graphene oxide (GO) used as green catalysts for copper(II) complex mediated click reaction. Copper(II) Bis(2,2′‐bipyridine) [CuII (bpy)2] (C1) and Copper(II) Bis(1,10‐phenanthroline) [CuII (phen)2] (C2) have synthesized for the intercalation of corresponding nanocomposites with GO, [GO@CuII (bpy)2] (GO‐C1) and [GO@CuII (phen)2] (GO‐C2). The noncovalent interaction of complexes supported on the surface of the GO nanosheets proves as an evident active site to facilitate the enhanced catalytic activity of copper‐catalyzed alkyne azide cycloaddition (CuIIAAC) reaction for the isolation of 1,4‐disubstituted‐1,2,3‐triazoles as click products in shorter reaction time with 80%–91% yield (five examples). The X‐ray diffraction (XRD) pattern of these composites shows the enhanced interlayers d‐spacing range of 1.01–1.12 nm due to the intercalation of copper(II) complexes in between the GO basal planes and characterized by X‐ray photoelectron spectroscopy (XPS), Fourier‐transform infrared spectroscopy (FT‐IR), Raman, UV, scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The as‐prepared nanocomposites were employed for the typical click reactions using the substrates of azide and acetylene. These classes of composite materials can be referred to recyclable, heterogeneous, green catalysts with high atom economy and could also be used for the isolation of click products in biomolecules.

show abstract

“…The [Cu II (L 1 ‐L 3 )] complexes were synthesized by the addition of corresponding ligands to the Cu(II) precursor in the ratio of 1:2 mole equivalents (1:1 in the case of L 3 ligand) . The formation of Cu(II) complexes (Cu II (L 1 ‐L 3 )) were confirmed by ESI‐MS.…”

Section: Resultsmentioning

confidence: 99%

Facile Synthesis of 1,4‐Disubstituted 1,2,3‐Triazoles Using Tetraaza‐coordinated Copper(II) Complexes as Efficient Catalysts

Samuel

2020

ChemistrySelect

View full text Add to dashboard Cite

We report the class of tetraaza coordinated copper(II) complexes of 1,10‐phenanthroline ([CuII(L1)2]ClO4), 2,2’‐bipyridine ([CuII(L2)2]ClO4) and 1,4,7,10‐tetraazacyclo‐dodecane ([CuII(L3)](ClO4)2) are employed as efficient catalysts for the Copper Catalyzed Azide Acetylene Cycloaddition (CuIIAAC) reaction. The complex [CuII(L1)2]ClO4 showed high catalytic activity with the reductant for [3+2] Huisgen cycloaddition of terminal alkyne and various azides due to its structural orientation. The corresponding 1,4‐disubstituted‐1,2,3‐triazoles are isolated in good yield (12 examples) at room temperature without the impact of additives. These complexes also facilitate the stabilization of in‐situ generated Cu(I)L species to a greater extent due to their ligand framework.

show abstract

Crystal structure of (perchlorato-κO)(1,4,7,10-tetraazacyclododecane-κ⁴N)copper(II) perchlorate

Abstract: The crystal structure of (perchlorato-κO)(1,4,7,10-tetraazacyclododecane-κ4 N)copper(II) perchlorate is reported. The crystal was grown from a solution of methanol at ambient temperature which resulted in no co-crystallization of solvent.

Cited by 4 publications

References 15 publications

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in ^64/67Cu Radiopharmaceuticals

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in ^64/67Cu Radiopharmaceuticals

Copper(II) complex intercalated graphene oxide nanocomposites as versatile, reusable catalysts for click reaction

Facile Synthesis of 1,4‐Disubstituted 1,2,3‐Triazoles Using Tetraaza‐coordinated Copper(II) Complexes as Efficient Catalysts

Contact Info

Product

Resources

About

Crystal structure of (perchlorato-κO)(1,4,7,10-tetraazacyclododecane-κ4N)copper(II) perchlorate

Abstract: The crystal structure of (perchlorato-κO)(1,4,7,10-tetra­aza­cyclo­dodecane-κ4 N)copper(II) perchlorate is reported. The crystal was grown from a solution of methanol at ambient temperature which resulted in no co-crystallization of solvent.

Cited by 4 publications

References 15 publications

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in 64/67Cu Radiopharmaceuticals

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in 64/67Cu Radiopharmaceuticals

Copper(II) complex intercalated graphene oxide nanocomposites as versatile, reusable catalysts for click reaction

Facile Synthesis of 1,4‐Disubstituted 1,2,3‐Triazoles Using Tetraaza‐coordinated Copper(II) Complexes as Efficient Catalysts

Contact Info

Product

Resources

About

Crystal structure of (perchlorato-κO)(1,4,7,10-tetraazacyclododecane-κ⁴N)copper(II) perchlorate

Abstract: The crystal structure of (perchlorato-κO)(1,4,7,10-tetraazacyclododecane-κ4 N)copper(II) perchlorate is reported. The crystal was grown from a solution of methanol at ambient temperature which resulted in no co-crystallization of solvent.

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in ^64/67Cu Radiopharmaceuticals

Copper Coordination Chemistry of Sulfur Pendant Cyclen Derivatives: An Attempt to Hinder the Reductive-Induced Demetalation in ^64/67Cu Radiopharmaceuticals