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Title: A [Cyclentetrakis(methylene)]tetrakis[2-hydroxybenzamide]Ligand That Complexes and Sensitizes Lanthanide(III) Ions

Abstract

The synthesis of a cyclen derivative containing four isophthalamide groups (L{sup 1}) is described. The spectroscopic properties of the Ln(III) complexes of L{sup 1} (Ln = Gd, Tb, Yb, Eu) reveal changes of the UV/visible absorption, circular dichroism absorption, luminescence and circularly polarized luminescence properties. It is shown that at least two metal complex species are present in solution, whose relative amounts are pH dependent. When at pH > 8.0, an intense long lived emission is observed (for [L{sup 1}Tb] and [L{sup 1}Yb]) while at pH < 8.0, a weaker, shorter-lived species predominates. Unconventional Ln(III) emitters (Pr, Nd, Sm, Dy and Tm) were sensitized in basic solution, both in the visible and in the near infra-red, to measure the emission of these ions.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Chemical Sciences Division
OSTI Identifier:
993491
Report Number(s):
LBNL-2881E
Journal ID: ISSN 0018-019X; HCACAV; TRN: US201023%%494
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Helvetica Chimica Acta; Journal Volume: 92; Journal Issue: 11
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ABSORPTION; DICHROISM; LUMINESCENCE; SYNTHESIS

Citation Formats

D'Aleo, Anthony, Xu, Jide, Do, King, Muller, Gilles, and Raymond, Kenneth N. A [Cyclentetrakis(methylene)]tetrakis[2-hydroxybenzamide]Ligand That Complexes and Sensitizes Lanthanide(III) Ions. United States: N. p., 2009. Web. doi:10.1002/hlca.200900161.
D'Aleo, Anthony, Xu, Jide, Do, King, Muller, Gilles, & Raymond, Kenneth N. A [Cyclentetrakis(methylene)]tetrakis[2-hydroxybenzamide]Ligand That Complexes and Sensitizes Lanthanide(III) Ions. United States. doi:10.1002/hlca.200900161.
D'Aleo, Anthony, Xu, Jide, Do, King, Muller, Gilles, and Raymond, Kenneth N. 2009. "A [Cyclentetrakis(methylene)]tetrakis[2-hydroxybenzamide]Ligand That Complexes and Sensitizes Lanthanide(III) Ions". United States. doi:10.1002/hlca.200900161. https://www.osti.gov/servlets/purl/993491.
@article{osti_993491,
title = {A [Cyclentetrakis(methylene)]tetrakis[2-hydroxybenzamide]Ligand That Complexes and Sensitizes Lanthanide(III) Ions},
author = {D'Aleo, Anthony and Xu, Jide and Do, King and Muller, Gilles and Raymond, Kenneth N.},
abstractNote = {The synthesis of a cyclen derivative containing four isophthalamide groups (L{sup 1}) is described. The spectroscopic properties of the Ln(III) complexes of L{sup 1} (Ln = Gd, Tb, Yb, Eu) reveal changes of the UV/visible absorption, circular dichroism absorption, luminescence and circularly polarized luminescence properties. It is shown that at least two metal complex species are present in solution, whose relative amounts are pH dependent. When at pH > 8.0, an intense long lived emission is observed (for [L{sup 1}Tb] and [L{sup 1}Yb]) while at pH < 8.0, a weaker, shorter-lived species predominates. Unconventional Ln(III) emitters (Pr, Nd, Sm, Dy and Tm) were sensitized in basic solution, both in the visible and in the near infra-red, to measure the emission of these ions.},
doi = {10.1002/hlca.200900161},
journal = {Helvetica Chimica Acta},
number = 11,
volume = 92,
place = {United States},
year = 2009,
month = 4
}
  • 1,4,7,10-tetrakis(2-hydroxyethyl)-1,4,7,10-tetraazacyclododecane(THED) and (1S,4S,7S,10S)-1,4,7,10-tetrakis(2hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) complexes of lanthanides were evaluated with their ability to promote transesterification of the 4-nitrophenyl phosphate ester of propylene glycol (1) or the cleavage of RNA oligomers. Kinetics of the reactions were measured and rate constants are reported.
  • The kinetics of the exchange reactions of N-deuterated ethylenediamine with paramagnetic Ln(en-d[sub 4])[sub 4][sup 3+] (Ln[sup 3+] = Pr[sup 3+], Nd[sup 3+], Eu[sup 3+], Er[sup 3+], Yb[sup 3+]) complexes in deuterated acetonitrile were investigated over the temperature range 233-343 K using [sup 1]H NMR. The data were analyzed by line shape analysis using the equation for a two-site exchange. The mean ligand residence times, [tau][sub m], were observed to increase across the lanthanide series. The erbium and ytterbium systems demonstrated both the slow- and fast-exchange limits over this temperature range on both the 300- and 100-MHz time scales; however, exchangemore » involving complexes of the large metal ions revealed coalescence of the coordinated and free ligand peaks even at the lowest temperature studied (233 K). A linear dependency of 1/[tau][sub m] on the concentration of free ligand was observed for complexes derived from the larger ions (Pr[sup 3+], Nd[sup 3+], Eu[sup 3+]), corresponding to a rate law that is first order in ethylenediamine concentration. The mechanism proposed for these reactions is discussed in terms of a nine-coordinate intermediate. For complexes of the smaller ions (Ln[sup 3+] = Er[sup 3+], Yb[sup 3+]), 1/[tau][sub m] was nearly independent of the ethylenediamine concentration at higher temperatures and revealed a nonlinear dependency on ethylenediamine concentration at lower temperatures. Parallel I[sub d] and D exchange mechanisms are proposed to be operating in these systems. 29 refs., 6 figs., 1 tab.« less
  • The ratio of the band intensities of the luminescence spectra of lanthanide ions (Ln) - which equals one, corresponding to the so-called ''supersensitive'' transition (SST) (with a difference of the quantum numbers J of the electronic states ..delta..J = 2), and the other which does not correspond to it or which corresponds to the magnetic dipole transition - is an important value which is dependent on the environment of Ln/sup 3 +/. For a number of europium complexes such values, denoted in the sequel by n, have been determined in prior work, in which references are given to still earliermore » studies. The values of n for Eu in a series of glasses are available. A correlation has been established between the values of n for Sm/sup 3 +/ and Eu/sup 3 +/ and the intensity of the absorption bands, established by the oscillator strenghts (P) of Nd/sup 3 +/ ions in solutions of analogous complexes; a similar dependence is found between the values of n for Tb and Dy and the P values in solutions of Ho/sup 3 +/ complexes. It has been found that the value of n increases in the majority of cases in direct proportion of the number of coordinated ligands. The ratios of the band intensities of the luminescence spectra depend also on the type of solvent in which the complexes are dissolved and grow with increase in its dielectric constant.« less
  • Lanthanide-induced shifts (LIS) in the NMR spectra of lanthanide(III) complexes derived from 1,4,7,10-tetrakis(N,N-diethylacetamido)-1,4,7,10-tetraazacyclododecane. Linear least-squares analysis was used to interpret the data. Molecular mechanics combined with LIS algorithms were used to calculate the solution structures of the complexes. Molecular structure parameters are presented.
  • Solution and solid-state properties of the Eu(III) complex of the tetramide macrocyclic ligand TCMC (TCMC = 1,4,7,10-tetrakis(carbamoylmethyl)-1,4-7,10-tetraazacyclododecane) are investigated as part of an effort to develop lanthanide(III) macrocyclic catalysts. (Eu(TCMC)(H{sub 2}O))(CF{sub 3}SO{sub 3}){sub 3}{center_dot}2CH{sub 3}OH crystallizes in the centrosymmetric monoclinic space group. The structure was solved and refined to R=4.02% and R{sub w}=4.33% for 3510 reflections with F>6{omega}(F). (R=7.04%, R{sub w}=6.48% for all 5322 independent reflections). Four stereoisomers (two enantiomeric pairs) of the (Eu(TCMC)(H{sub 2}O)){sup 3+} cation appear in the crystal. The structure is disordered, containing two overlapping diastereomers that are interrelated by different conformations of the 1,4,7,10-tetraazacyclododecane ring definingmore » the asymmetric unit. Two enantiomers are related to these by operations of the second king (i,n-glide). The nine-coordinate Eu(III) center has a 4:4:1 coordination geometry formed by the octadentate TCMC ligand and a single bound water molecule. The laser-induced luminescence excitation band of a single crystal of (Eu(TCMC)H{sub 2}O)(CF{sub 3}SO{sub 3}){sub 3}{center_dot}2CH{sub 3}OH resolves into two peaks, suggesting that each diastereomer gives rise to a separate excitation peak. Similarly, the luminescence excitation spectrum of a solution of (Eu(TCMC)){sup 3+} in water indicates that two species are present in solution. The {sup 31}P NMR resonance of diethyl phosphate is monitored at 18{+-}2{degrees}C, pH 7.4, upon addition of (Eu(TCMC)){sup 3+} as well as upon addition of several lanthanide(III) complexes that are catalysts for RNA cleavage. No binding of diethyl phosphate to (Eu(TCMC)){sup 3+} is observed. The hexadentate Schiff-base complex (La(L{sup 1})){sup 3+} binds to diethyl phosphate with a binding constant of 47.7{+-}0.5 M{sup -1}.« less