DOTA complexes with divalent zinc, cadmium and mercury: X-ray and solid-state NMR studies and solution isomerism
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61389013%3A_____%2F25%3A00641336" target="_blank" >RIV/61389013:_____/25:00641336 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11310/25:10505990
Result on the web
<a href="https://pubs.rsc.org/en/content/articlelanding/2025/dt/d5dt01880c" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2025/dt/d5dt01880c</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/D5DT01880C" target="_blank" >10.1039/D5DT01880C</a>
Alternative languages
Result language
angličtina
Original language name
DOTA complexes with divalent zinc, cadmium and mercury: X-ray and solid-state NMR studies and solution isomerism
Original language description
DOTA is widely regarded as a “prototype chelator” in the coordination chemistry of macrocyclic ligands. Its macrocyclic cavity can adapt to the size and coordination requirements of various metal ions. However, its complexes with divalent metal ions have been less explored than those with trivalent ions. Here, we studied the complexes of d10 metal ions, Zn(II), Cd(II) and Hg(II), which are chemically similar but have different ionic radii and prefer different coordination numbers (CNs). Solid-state structures of the [M(dota)]2− anions show different coordination modes going from an octahedron and CN 6 for Zn(II) to a twisted-square antiprismatic (TSA) arrangement with CN (6 + 2) for Cd(II) and CN (6 + 1)/(6 + 2) for Hg(II). The coordination spheres are distorted from the ideal arrangements, and they consist of four amine groups (forming an N4 plane) and 2–4 oxygen atoms of the carboxylate pendant arms. The oxygen atoms of the pendant arms are also bound to Ba(II) or Ca(II) counter-ions in various metal-ion bridging modes. The 13C and 15N solid-state NMR data correspond well to the structures determined by X-ray diffraction. The fluxionality of the coordination sphere was investigated by variable-temperature 13C NMR spectroscopy in solution. The measurements pointed to a higher rigidity of the macrocycle chelate rings compared to those formed by the pendant arms. The pendants are highly fluxional due to the easy change of their coordination modes as was observed in the solid state. Overall, the results confirm the size-dependent coordination behaviour of the internal cavity of DOTA-like macrocycles, which differs significantly from those observed in complexes of trivalent metal ions, e.g. trivalent lanthanides.
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
Result was created during the realization of more than one project. More information in the Projects tab.
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
44
Country of publishing house
GB - UNITED KINGDOM
Number of pages
15
Pages from-to
16535-16549
UT code for WoS article
001599320600001
EID of the result in the Scopus database
2-s2.0-105021352695