DOTA complexes with divalent zinc, cadmium and mercury: X-ray and solid-state NMR studies and solution isomerism

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/00216208:11310/25:10505990

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

DOTA complexes with divalent zinc, cadmium and mercury: X-ray and solid-state NMR studies and solution isomerism

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

DOTA complexes with divalent zinc, cadmium and mercury: X-ray and solid-state NMR studies and solution isomerism

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

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

44

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

15

Strana od-do

16535-16549

Kód UT WoS článku

001599320600001

EID výsledku v databázi Scopus

2-s2.0-105021352695