Structural aspects of copper catalyzed atom transfer radical polymerization

A series of 1,4,8,11-tetraazabicyclo[6.6.2]hexadecane ligands, including the parent compound, N,N‘-dialkyl variants, and the first N,N‘-di-pendant-arm derivatives have been synthesized by a short, efficient, and conceptually novel approach. Their copper(II) complexes have been prepared, and four of these were structurally characterized by X-ray diffraction. In all four complexes, the cross-bridged tetraamine ligand was found to be cis-folded, coordinating the metal cation within its molecular cleft using all four nitrogen lone pairs. Geometries intermediate between idealized square pyramidal and trigonal bipyramidal coordination were found for three of the complexes, whereas a distorted octahedral copper coordination was found for the complex of a di-pendant-arm cross-bridged cyclam.

Synthesis and Characterization of Cross-Bridged Cyclams and Pendant-Armed Derivatives and Structural Studies of Their Copper(II) Complexes

A new fluorescent nanosensor family for Zn2+ determination is reported based on azamacrocycle derivatization of CdSe/ZnS core/shell quantum dot nanoparticles. They are the first zinc ion sensors using QD nanoparticles in a host−guest and receptor−fluorophore system. Three azamacrocycles are demonstrated as receptors: TACN (1,4,7-triazacyclononane), cyclen (1,4,7,10-tetraazacyclododecane), and cyclam (1,4,8,11-tetraazacyclotetradecane). Azamacrocycles conjugated to QDs via an amide link interact directly with one of the photoinduced QD charge carriers, probably transferring the hole in the QD to the azamacrocycle, thereby disrupting the radiative recombination process. When zinc ion enters the aza-crown, the lone pair electrons of the nitrogen atom become involved in the coordination and the energy level is no longer available for the hole-transfer mechanism, switching on the QD emission and a dramatic increase of the fluorescence intensity results, allowing the detection of low concentrations of zinc ions...

Azamacrocycle activated quantum dot for zinc ion detection.

Phthalocyanines Containing Macrocycles

Electrochemical and spectroscopic studies on copper(II) complexes of macrocyclic ligands as models for square-pyramidal metal active sites of copper(II) complexes of bleomycin and glutathione

R. C. Smierciak

Papers

Copper(II) complexes containing a 12-membered macrocyclic ligand

Copper(ii) complexes containing a 12-membered macrocyclic ligand

A comparative study of steric effects of nickel(II) complexes containing 12-membered macrocyclic ligands

A comparative study of steric effects of nickel(ii) complexes containing 12‐membered macrocyclic ligands