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.

Basic information

Original name

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

Authors

LIMA, Luis M.P. (620 Portugal), Rita DELGADO (620 Portugal), Petr HERMANN (203 Czech Republic, guarantor), Radek ŠEVČÍK (203 Czech Republic, belonging to the institution), Přemysl LUBAL (203 Czech Republic, belonging to the institution), Henrique F. CARVALHO (620 Portugal), André F. MARTINS (620 Portugal), Éva TÓTH (250 France) and Carlos F.G.C. GERALDES (620 Portugal)

Edition

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

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

United Kingdom of Great Britain and Northern Ireland

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 3.120

RIV identification code

RIV/00216224:14740/12:00060069

Organization unit

Central European Institute of Technology

DOI

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

UT WoS

000303987800009

Keywords in English

macrocyclic ligands; lanthanide complexes; thermodynamics; kinetics; relaxivity

Abstract

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.

Links

ED1.1.00/02.0068, research and development project

Name: CEITEC - central european institute of technology

ME09065, research and development project

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

Investor: Ministry of Education, Youth and Sports of the CR, Research of new detection systems based on sensor arrays for application in speciation analysis, Research and Development Programme KONTAKT (ME)

Citovat

LIMA, Luis M.P., Rita DELGADO, Petr HERMANN, Radek ŠEVČÍK, Přemysl LUBAL, Henrique F. CARVALHO, André F. MARTINS, Éva TÓTH and 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, vol. 2012, No 15, p. 2548-2559. ISSN 1099-0682. Available from: 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 and 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, vol.~2012, No~15, p.~2548-2559. ISSN~1099-0682. Available from: https://dx.doi.org/10.1002/ejic.201101335.

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