Variation of water exchange dynamics with ligand structure and stereochemistry in lanthanide complexes based on 1,4-diazepine derivatives

Elisa M. Elemento; David Parker; Silvio Aime; Eliana Gianolio; Luciano Lattuada

doi:10.1039/b818445c

Variation of water exchange dynamics with ligand structure and stereochemistry in lanthanide complexes based on 1,4-diazepine derivatives

Elisa M. Elemento, David Parker^*, Silvio Aime, Eliana Gianolio, Luciano Lattuada

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

34 Citations (Scopus)

Abstract

Complexes of Gd, Eu and Yb(iii) have been prepared with a series of heptadentate ligands related to the parent complex AAZTA, based on the 6-methyl-6-aminoperhydrodiazepine moiety. For (RR) and (RS)-diastereoisomers of a di-glutarate ligand, solution NMR studies revealed the presence of two major species that undergo water exchange rates at Gd differing by a factor of six. Comparison of solution hydration states for Eu(iii) complexes reveals that each complex possesses two bound water molecules. The absence of a good correlation of ¹H NMR pseudo-contact shifts for Eu and Yb analogues is suggested to arise from a change in hydration state between Eu and Yb.

Original language	English
Pages (from-to)	1120-1131
Number of pages	12
Journal	Organic and Biomolecular Chemistry
Volume	7
Issue number	6
Early online date	30 Jan 2009
DOIs	https://doi.org/10.1039/b818445c
Publication status	Published - 21 Mar 2009

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title = "Variation of water exchange dynamics with ligand structure and stereochemistry in lanthanide complexes based on 1,4-diazepine derivatives",

abstract = "Complexes of Gd, Eu and Yb(iii) have been prepared with a series of heptadentate ligands related to the parent complex AAZTA, based on the 6-methyl-6-aminoperhydrodiazepine moiety. For (RR) and (RS)-diastereoisomers of a di-glutarate ligand, solution NMR studies revealed the presence of two major species that undergo water exchange rates at Gd differing by a factor of six. Comparison of solution hydration states for Eu(iii) complexes reveals that each complex possesses two bound water molecules. The absence of a good correlation of 1H NMR pseudo-contact shifts for Eu and Yb analogues is suggested to arise from a change in hydration state between Eu and Yb.",

author = "Elemento, {Elisa M.} and David Parker and Silvio Aime and Eliana Gianolio and Luciano Lattuada",

note = "We thank EPSRC, the Royal Society, the EC-networks, EMIL and DIMI and the ESF-COST Action D-38 for support. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2009",

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T1 - Variation of water exchange dynamics with ligand structure and stereochemistry in lanthanide complexes based on 1,4-diazepine derivatives

AU - Elemento, Elisa M.

AU - Parker, David

AU - Aime, Silvio

AU - Gianolio, Eliana

AU - Lattuada, Luciano

N1 - We thank EPSRC, the Royal Society, the EC-networks, EMIL and DIMI and the ESF-COST Action D-38 for support. Publisher Copyright: © The Royal Society of Chemistry 2009

PY - 2009/3/21

Y1 - 2009/3/21

N2 - Complexes of Gd, Eu and Yb(iii) have been prepared with a series of heptadentate ligands related to the parent complex AAZTA, based on the 6-methyl-6-aminoperhydrodiazepine moiety. For (RR) and (RS)-diastereoisomers of a di-glutarate ligand, solution NMR studies revealed the presence of two major species that undergo water exchange rates at Gd differing by a factor of six. Comparison of solution hydration states for Eu(iii) complexes reveals that each complex possesses two bound water molecules. The absence of a good correlation of 1H NMR pseudo-contact shifts for Eu and Yb analogues is suggested to arise from a change in hydration state between Eu and Yb.

AB - Complexes of Gd, Eu and Yb(iii) have been prepared with a series of heptadentate ligands related to the parent complex AAZTA, based on the 6-methyl-6-aminoperhydrodiazepine moiety. For (RR) and (RS)-diastereoisomers of a di-glutarate ligand, solution NMR studies revealed the presence of two major species that undergo water exchange rates at Gd differing by a factor of six. Comparison of solution hydration states for Eu(iii) complexes reveals that each complex possesses two bound water molecules. The absence of a good correlation of 1H NMR pseudo-contact shifts for Eu and Yb analogues is suggested to arise from a change in hydration state between Eu and Yb.

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JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

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Variation of water exchange dynamics with ligand structure and stereochemistry in lanthanide complexes based on 1,4-diazepine derivatives

Abstract

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