TY - JOUR
T1 - DOTP versus DOTA as Ligands for Lanthanide Cations
T2 - Novel Structurally Characterized CeIV and CeIII Cyclen-Based Complexes and Clusters in Aqueous Solutions
AU - Dovrat, Gev
AU - Pevzner, Svetlana
AU - Maimon, Eric
AU - Vainer, Radion
AU - Iliashevsky, Olga
AU - Ben-Eliyahu, Yeshayahu
AU - Moisy, Philippe
AU - Bettelheim, Armand
AU - Zilbermann, Israel
N1 - Publisher Copyright:
© 2022 Wiley-VCH GmbH.
PY - 2022/11/2
Y1 - 2022/11/2
N2 - The coordination and redox chemistry of aqueous CeIV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetraacetic acid and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite-like [CeIV6(O)4(OH)4(H2O)8(DOTAH)4] oxo-hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in-cage complexes [CeIVDOTP] and [CeIIIDOTP(H2O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in-cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above-mentioned species, the in-cage [CeIVDOTA(H2O)] complex structure is presented herein for the first time. An elaborative analysis of the X-ray crystallographic structural data obtained for the in-cage complexes studied herein and similar structures published previously suggests that hard-bonding cyclen-derived ligands are, counter-intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of LnII and AcIII cations.
AB - The coordination and redox chemistry of aqueous CeIV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetraacetic acid and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite-like [CeIV6(O)4(OH)4(H2O)8(DOTAH)4] oxo-hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in-cage complexes [CeIVDOTP] and [CeIIIDOTP(H2O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in-cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above-mentioned species, the in-cage [CeIVDOTA(H2O)] complex structure is presented herein for the first time. An elaborative analysis of the X-ray crystallographic structural data obtained for the in-cage complexes studied herein and similar structures published previously suggests that hard-bonding cyclen-derived ligands are, counter-intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of LnII and AcIII cations.
KW - cerium
KW - cluster compounds
KW - coordination chemistry
KW - macrocyclic ligands
KW - redox chemistry
KW - structure
UR - http://www.scopus.com/inward/record.url?scp=85139436140&partnerID=8YFLogxK
U2 - 10.1002/chem.202201868
DO - 10.1002/chem.202201868
M3 - Article
C2 - 36102009
AN - SCOPUS:85139436140
SN - 0947-6539
VL - 28
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 61
M1 - e202201868
ER -