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

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.

Přehled o publikaci