The solid-state structures and ligand cavity evaluation of lanthanide(III) complexes of a DOTA analogue with a (dibenzylamino)methylphosphinate pendant arm

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F20%3A10412394" target="_blank" >RIV/00216208:11310/20:10412394 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=N04XdGlH~P" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=N04XdGlH~P</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c9dt04056k" target="_blank" >10.1039/c9dt04056k</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The solid-state structures and ligand cavity evaluation of lanthanide(III) complexes of a DOTA analogue with a (dibenzylamino)methylphosphinate pendant arm

Popis výsledku v původním jazyce

A series of lanthanide(III) complexes of a monophosphinate analogue of H(4)dota, 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic-10-methyl[(N,N-dibenzylamino)methyl]phosphinic acid (H(4)do3ap(DBAm) = H(4)L1), were prepared and their solid-state structures were studied using single-crystal X-ray diffraction. In all structures, the ligand anion was octadentately coordinated to the Ln(III) or Sc(III) ions similarly to other DOTA-like ligands, i.e. forming parallel N-4- and O-4-planes. The lighter lanthanide(III) complexes (till dysprosium) were nonacoordinated in the twisted square-antiprismatic (TSA) configuration with the apical coordination of water molecules or oxygen atoms from the neighbouring complex unit. The heavier lanthanide(III) complexes (from terbium) were found as the &quot;anhydrous&quot; octacoordinated twisted square-antiprismatic (TSA&apos;) isomer. For the terbium(III) ion, both forms were structurally characterized. The structural data of the Ln(III)-H(4)L1 complexes and complexes of several related DOTA-like ligands were analysed. It clearly showed that the structural parameters for the square-antiprismatic (SA) isomers were clustered in a small range while those for the TSA/TSA&apos; isomers were significantly more spread. The analysis also gave useful information about the influence of various pendant arms on the structure of the complexes of the DOTA-like ligands. The twist angle (torsion) of the chelate ring containing a larger phosphorus atom was similar to those of the remaining three acetate pendants. It led to a larger separation of the N4O4 planes and to smaller trans-O-Ln-O angles than the parameters found in the complexes of H(4)dota and its tetraamide derivatives dotam((R)). It resulted in a relatively long bond between the metal ion and the coordinated water molecule. It led, together with the negative charge of the oxygen atoms forming the O-4-plane, to an extremely fast water exchange rate reported for the Gd(III)-H(4)L1 complex and, generally, to a fast water exchange of Gd(III) complexes with the monophosphorus acid analogues of H(4)dota, H(5)do3ap/H(4)do3ap(R).

Název v anglickém jazyce

The solid-state structures and ligand cavity evaluation of lanthanide(III) complexes of a DOTA analogue with a (dibenzylamino)methylphosphinate pendant arm

Popis výsledku anglicky

A series of lanthanide(III) complexes of a monophosphinate analogue of H(4)dota, 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic-10-methyl[(N,N-dibenzylamino)methyl]phosphinic acid (H(4)do3ap(DBAm) = H(4)L1), were prepared and their solid-state structures were studied using single-crystal X-ray diffraction. In all structures, the ligand anion was octadentately coordinated to the Ln(III) or Sc(III) ions similarly to other DOTA-like ligands, i.e. forming parallel N-4- and O-4-planes. The lighter lanthanide(III) complexes (till dysprosium) were nonacoordinated in the twisted square-antiprismatic (TSA) configuration with the apical coordination of water molecules or oxygen atoms from the neighbouring complex unit. The heavier lanthanide(III) complexes (from terbium) were found as the &quot;anhydrous&quot; octacoordinated twisted square-antiprismatic (TSA&apos;) isomer. For the terbium(III) ion, both forms were structurally characterized. The structural data of the Ln(III)-H(4)L1 complexes and complexes of several related DOTA-like ligands were analysed. It clearly showed that the structural parameters for the square-antiprismatic (SA) isomers were clustered in a small range while those for the TSA/TSA&apos; isomers were significantly more spread. The analysis also gave useful information about the influence of various pendant arms on the structure of the complexes of the DOTA-like ligands. The twist angle (torsion) of the chelate ring containing a larger phosphorus atom was similar to those of the remaining three acetate pendants. It led to a larger separation of the N4O4 planes and to smaller trans-O-Ln-O angles than the parameters found in the complexes of H(4)dota and its tetraamide derivatives dotam((R)). It resulted in a relatively long bond between the metal ion and the coordinated water molecule. It led, together with the negative charge of the oxygen atoms forming the O-4-plane, to an extremely fast water exchange rate reported for the Gd(III)-H(4)L1 complex and, generally, to a fast water exchange of Gd(III) complexes with the monophosphorus acid analogues of H(4)dota, H(5)do3ap/H(4)do3ap(R).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/LTC17067" target="_blank" >LTC17067: Využití NMR relaxačních a difúzních měření pro stanovení dynamiky komplexních molekulárních systémů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

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

—

Svazek periodika

49

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

15

Strana od-do

1555-1569

Kód UT WoS článku

000527532000021

EID výsledku v databázi Scopus

2-s2.0-85079076463