Unusual variability of isomers in copper(ii) complexes with 1,8-bis(2-hydroxybenzyl)-cyclam

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00617190" target="_blank" >RIV/61388963:_____/25:00617190 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/25:00617190 RIV/00216208:11310/25:10500138

Výsledek na webu

<a href="https://doi.org/10.1039/D4DT03166K" target="_blank" >https://doi.org/10.1039/D4DT03166K</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4dt03166k" target="_blank" >10.1039/d4dt03166k</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Unusual variability of isomers in copper(ii) complexes with 1,8-bis(2-hydroxybenzyl)-cyclam

Popis výsledku v původním jazyce

Copper isotopes and their complexes are intensively studied due to their high potential for applications in radiodiagnosis and radiotherapy. Here, we study the CuII complex of 1,8-bis(2-hydroxybenzyl)-cyclam (H2L), which forms an unexpected variety of isomers differing in the mutual orientation of the substituents on the cyclam nitrogen atoms, the protonation of the phenolate pendant, and the ligand denticity. The interconversion of the isomers is rather slow, which made the isolation, identification and investigation of some of the individual species possible. The most stable and the most common form is the hexacoordinated trans-III isomer. However, several other forms were also observed in solution in the course of HPLC, UV-VIS and electrochemical measurements. The isomers present in solution were identified by comparison with the solid-state structures solved by X-ray diffraction analysis on single crystals and with the help of theoretical calculations. The phenolate pendant is coordinated both in the protonated and deprotonated state, however, the coordination in the axial position of the hexacoordinated trans-III complex is weak, especially in its protonated state. Conversely, the CuII ion is pentacoordinated in the cis-V isomer with only one phenolate strongly coordinated in the basal plane of the distorted tetragonal pyramid. The computational data showed that the phenolate groups might form strong intraligand hydrogen bonds competitive with the metal-phenolate bonds, stabilizing the structure of the complex. In addition, theoretical calculations revealed that several geometries are energetically close to the optimal one, which indicates possible dynamic behaviour of the complex in solution.

Název v anglickém jazyce

Unusual variability of isomers in copper(ii) complexes with 1,8-bis(2-hydroxybenzyl)-cyclam

Popis výsledku anglicky

Copper isotopes and their complexes are intensively studied due to their high potential for applications in radiodiagnosis and radiotherapy. Here, we study the CuII complex of 1,8-bis(2-hydroxybenzyl)-cyclam (H2L), which forms an unexpected variety of isomers differing in the mutual orientation of the substituents on the cyclam nitrogen atoms, the protonation of the phenolate pendant, and the ligand denticity. The interconversion of the isomers is rather slow, which made the isolation, identification and investigation of some of the individual species possible. The most stable and the most common form is the hexacoordinated trans-III isomer. However, several other forms were also observed in solution in the course of HPLC, UV-VIS and electrochemical measurements. The isomers present in solution were identified by comparison with the solid-state structures solved by X-ray diffraction analysis on single crystals and with the help of theoretical calculations. The phenolate pendant is coordinated both in the protonated and deprotonated state, however, the coordination in the axial position of the hexacoordinated trans-III complex is weak, especially in its protonated state. Conversely, the CuII ion is pentacoordinated in the cis-V isomer with only one phenolate strongly coordinated in the basal plane of the distorted tetragonal pyramid. The computational data showed that the phenolate groups might form strong intraligand hydrogen bonds competitive with the metal-phenolate bonds, stabilizing the structure of the complex. In addition, theoretical calculations revealed that several geometries are energetically close to the optimal one, which indicates possible dynamic behaviour of the complex in solution.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

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

2025

Kód důvěrnosti údajů

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

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

54

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

3127-3140

Kód UT WoS článku

001397682200001

EID výsledku v databázi Scopus

2-s2.0-85215840136