Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic
Stability, Kinetics, Solution Structure, and Relaxivity of
Ln(3+) Complexes

J 2012

Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln(3+) Complexes

LIMA, Luis M.P., Rita DELGADO, Petr HERMANN, Radek ŠEVČÍK, Přemysl LUBAL et. al.

Základní údaje

Originální název

Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln(3+) Complexes

Autoři

LIMA, Luis M.P. (620 Portugalsko), Rita DELGADO (620 Portugalsko), Petr HERMANN (203 Česká republika, garant), Radek ŠEVČÍK (203 Česká republika, domácí), Přemysl LUBAL (203 Česká republika, domácí), Henrique F. CARVALHO (620 Portugalsko), André F. MARTINS (620 Portugalsko), Éva TÓTH (250 Francie) a Carlos F.G.C. GERALDES (620 Portugalsko)

Vydání

Eur. J. Inorg. Chem. WEINHEIM, Wiley-VCH Verlag GMBH, 2012, 1099-0682

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 3.120

Kód RIV

RIV/00216224:14740/12:00060069

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1002/ejic.201101335

UT WoS

000303987800009

Klíčová slova anglicky

macrocyclic ligands; lanthanide complexes; thermodynamics; kinetics; relaxivity

Štítky

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 7. 2. 2018 18:52, prof. RNDr. Přemysl Lubal, Ph.D.

Anotace

V originále

The lanthanide (Ln3+) complexes of three cyclen-based ligands containing three methylphosphonate pendant arms were studied, the ligands being 1,4,7,10-tetraazacyclododecane-1,4,7-triyltris(methylphosphonic acid) (H6do3p), 3-[4,7,10-tris(phosphonomethyl)-1,4,7,10-tetraazacyclododec-1-yl]propanoic acid (H7do3p1pr), and 10-(3-hydroxypropyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triyltris(methylphosphonic acid) (H6do3p1ol). The three macrocyclic ligands form complexes of very high thermodynamic stability with all studied Ln3+ ions. Kinetic studies showed that the acid-assisted dissociation of Ce3+ complexes of these ligands is much faster than for the complex of the related ligand H8dotp [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayltetrakis(methylphosphonic acid)]. The number of water molecules coordinated to the Eu3+ and Gd3+ complexes was estimated to be < 1 for the do3p1ol ligand but ca. 1 for the other two ligands, as obtained by time-resolved luminescence spectroscopy and by 1H and 17O relaxometric measurements. The NMR spectroscopic data indicate the existence of a considerable contribution from second-sphere water molecules to the relaxivity of all the Gd3+ complexes studied. The 1H and 31P NMR spectra of the Eu3+, Yb3+ and Lu3+ complexes showed that the propionate arm in the [Ln(do3p1pr)]4 complexes and the propanol arm in the [Ln(do3p1ol)]3 complexes are not bound to the Ln3+ ion. The [Ln(do3p)]3 and [Ln(do3p1pr)]4 complexes have a clear preference for the TSAP (twisted square antiprismatic) isomer, while both SAP (square antiprismatic) and TSAP isomers are present in solutions of the [Ln(do3p1ol)]3 complexes.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

ME09065, projekt VaV

Název: Výzkum nových detekčních systémů na bázi senzorových polí pro použití ve speciační analýze

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Výzkum nových detekčních systémů na bázi senzorových polí pro použití ve speciační analýze, Program výzkumu a vývoje KONTAKT (ME)

Citovat

LIMA, Luis M.P., Rita DELGADO, Petr HERMANN, Radek ŠEVČÍK, Přemysl LUBAL, Henrique F. CARVALHO, André F. MARTINS, Éva TÓTH a Carlos F.G.C. GERALDES. Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln(3+) Complexes. Eur. J. Inorg. Chem. WEINHEIM: Wiley-VCH Verlag GMBH, 2012, roč. 2012, č. 15, s. 2548-2559. ISSN 1099-0682. Dostupné z: https://dx.doi.org/10.1002/ejic.201101335.

@article{984031,
   author = {Lima, Luis M.P. and Delgado, Rita and Hermann, Petr and Ševčík, Radek and Lubal, Přemysl and Carvalho, Henrique F. and Martins, André F. and Tóth, Éva and Geraldes, Carlos F.G.C.},
   article_location = {WEINHEIM},
   article_number = {15},
   doi = {http://dx.doi.org/10.1002/ejic.201101335},
   keywords = {macrocyclic ligands; lanthanide complexes; thermodynamics; kinetics; relaxivity},
   language = {eng},
   issn = {1099-0682},
   journal = {Eur. J. Inorg. Chem.},
   title = {Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln(3+) Complexes},
   url = {http://onlinelibrary.wiley.com/doi/10.1002/ejic.201101335/abstract},
   volume = {2012},
   year = {2012}
}

TY  - JOUR
ID  - 984031
AU  - Lima, Luis M.P. - Delgado, Rita - Hermann, Petr - Ševčík, Radek - Lubal, Přemysl - Carvalho, Henrique F. - Martins, André F. - Tóth, Éva - Geraldes, Carlos F.G.C.
PY  - 2012
TI  - Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln(3+) Complexes
JF  - Eur. J. Inorg. Chem.
VL  - 2012
IS  - 15
SP  - 2548-2559
EP  - 2548-2559
PB  - Wiley-VCH Verlag GMBH
SN  - 10990682
KW  - macrocyclic ligands
KW  - lanthanide complexes
KW  - thermodynamics
KW  - kinetics
KW  - relaxivity
UR  - http://onlinelibrary.wiley.com/doi/10.1002/ejic.201101335/abstract
L2  - http://onlinelibrary.wiley.com/doi/10.1002/ejic.201101335/abstract
N2  - The lanthanide (Ln3+) complexes of three cyclen-based ligands containing three methylphosphonate pendant arms were studied, the ligands being 1,4,7,10-tetraazacyclododecane-1,4,7-triyltris(methylphosphonic acid) (H6do3p), 3-[4,7,10-tris(phosphonomethyl)-1,4,7,10-tetraazacyclododec-1-yl]propanoic acid (H7do3p1pr), and 10-(3-hydroxypropyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triyltris(methylphosphonic acid) (H6do3p1ol). The three macrocyclic ligands form complexes of very high thermodynamic stability with all studied Ln3+ ions. Kinetic studies showed that the acid-assisted dissociation of Ce3+ complexes of these ligands is much faster than for the complex of the related ligand H8dotp [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayltetrakis(methylphosphonic acid)]. The number of water molecules coordinated to the Eu3+ and Gd3+ complexes was estimated to be < 1 for the do3p1ol ligand but ca. 1 for the other two ligands, as obtained by time-resolved luminescence spectroscopy and by 1H and 17O relaxometric measurements. The NMR spectroscopic data indicate the existence of a considerable contribution from second-sphere water molecules to the relaxivity of all the Gd3+ complexes studied. The 1H and 31P NMR spectra of the Eu3+, Yb3+ and Lu3+ complexes showed that the propionate arm in the [Ln(do3p1pr)]4 complexes and the propanol arm in the [Ln(do3p1ol)]3 complexes are not bound to the Ln3+ ion. The [Ln(do3p)]3 and [Ln(do3p1pr)]4 complexes have a clear preference for the TSAP (twisted square antiprismatic) isomer, while both SAP (square antiprismatic) and TSAP isomers are present in solutions of the [Ln(do3p1ol)]3 complexes.
ER  -

LIMA, Luis M.P., Rita DELGADO, Petr HERMANN, Radek ŠEVČÍK, Přemysl LUBAL, Henrique F. CARVALHO, André F. MARTINS, Éva TÓTH a Carlos F.G.C. GERALDES. Tris(phosphonomethyl)cyclen Derivatives: Thermodynamic Stability, Kinetics, Solution Structure, and Relaxivity of Ln(3+) Complexes. \textit{Eur. J. Inorg. Chem.}. WEINHEIM: Wiley-VCH Verlag GMBH, 2012, roč.~2012, č.~15, s.~2548-2559. ISSN~1099-0682. Dostupné z: https://dx.doi.org/10.1002/ejic.201101335.

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