Unusual variability of isomers in copper(ii) complexes with 1,8-bis(2-hydroxybenzyl)-cyclam
The result's identifiers
Result code in 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>
Alternative codes found
RIV/61388955:_____/25:00617190 RIV/00216208:11310/25:10500138
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Unusual variability of isomers in copper(ii) complexes with 1,8-bis(2-hydroxybenzyl)-cyclam
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA21-23261S" target="_blank" >GA21-23261S: Interconnected azamacrocyclic complexes – new kind of molecular electronics</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
54
Issue of the periodical within the volume
8
Country of publishing house
GB - UNITED KINGDOM
Number of pages
14
Pages from-to
3127-3140
UT code for WoS article
001397682200001
EID of the result in the Scopus database
2-s2.0-85215840136