Copper(II) Complexes of Phenolate-Bridged Dimeric Cyclam Ligands: Synthesis, Coordination and Electrochemical Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00599913" target="_blank" >RIV/61388955:_____/24:00599913 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/24:10484160

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202400288" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202400288</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejic.202400288" target="_blank" >10.1002/ejic.202400288</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Copper(II) Complexes of Phenolate-Bridged Dimeric Cyclam Ligands: Synthesis, Coordination and Electrochemical Study

Popis výsledku v původním jazyce

Bis(macrocyclic) complexes are investigated as artificial analogues of natural dinuclear metalloenzymes. Two ligands containing two cyclam rings connected through a p-cresol or 4-nitrophenol spacer were synthesized and their complexing properties were investigated. CuII complexes were prepared and their properties were studied by a combination of spectral, diffraction and electrochemical methods. The phenolate group is not or only weakly coordinated to the central CuII ion and the two macrocycles behave mostly as two independent complexing units. All the determined solid-state structures showed cyclam adopting trans-III geometry, however, solution study indicated the presence of more isomers in the solution whose abundance changes with pH. Electrochemical reduction of the complexes is irreversible and results in the reductive decomplexation to amalgamated Cu metal. The amalgamated metal is re-oxidized to CuII during the anodic scan of CV and the metal ion is re-coordinated. The ligand containing the nitro group shows an irreversible four-electron reduction of the nitro group. The ligands and the complexes undergo also a slow degradation when incubated in the aqueous solutions for a prolonged time. The degradation relies on the “retro-Mannich” cleavage of the methylene bridge connecting the cyclam ring with the phenol moiety.

Název v anglickém jazyce

Copper(II) Complexes of Phenolate-Bridged Dimeric Cyclam Ligands: Synthesis, Coordination and Electrochemical Study

Popis výsledku anglicky

Bis(macrocyclic) complexes are investigated as artificial analogues of natural dinuclear metalloenzymes. Two ligands containing two cyclam rings connected through a p-cresol or 4-nitrophenol spacer were synthesized and their complexing properties were investigated. CuII complexes were prepared and their properties were studied by a combination of spectral, diffraction and electrochemical methods. The phenolate group is not or only weakly coordinated to the central CuII ion and the two macrocycles behave mostly as two independent complexing units. All the determined solid-state structures showed cyclam adopting trans-III geometry, however, solution study indicated the presence of more isomers in the solution whose abundance changes with pH. Electrochemical reduction of the complexes is irreversible and results in the reductive decomplexation to amalgamated Cu metal. The amalgamated metal is re-oxidized to CuII during the anodic scan of CV and the metal ion is re-coordinated. The ligand containing the nitro group shows an irreversible four-electron reduction of the nitro group. The ligands and the complexes undergo also a slow degradation when incubated in the aqueous solutions for a prolonged time. The degradation relies on the “retro-Mannich” cleavage of the methylene bridge connecting the cyclam ring with the phenol moiety.

Druh

J_SC - Článek v periodiku v databázi SCOPUS

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

<a href="/cs/project/GA21-23261S" target="_blank" >GA21-23261S: Propojené azamakrocyklické komplexy – nový druh molekulární elektroniky</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

European Journal of Inorganic Chemistry

ISSN

1434-1948

e-ISSN

1099-0682

Svazek periodika

27

Číslo periodika v rámci svazku

31

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

e202400288

Kód UT WoS článku

—

EID výsledku v databázi Scopus

2-s2.0-85206241354