The confluence of structure and dynamics in lanthanide(iii) chelates: how dynamics help define structure in solution
- 7 October 2013
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Dalton Transactions
- Vol. 43 (1), 251-258
- https://doi.org/10.1039/c3dt52143e
Abstract
Coordination exchange processes tend to dominate the solution state behaviour of lanthanide chelates and generally prohibit the study of small conformational changes. In this article we take advantage of coordinatively rigid Eu3+ chelates to examine the small conformational changes that occur in these chelates as water dissociatively exchanges in and out of the inner coordination sphere. The results show that the time-averaged conformation of the chelate alters as the water exchange rate increases. This conformational change reflects a change in the hydration state (q/rLnH 6) of the chelate. The hydration state has recently come to be expressed as two separate parameters q and rLnH. However, these two parameters simultaneously describe the same structural considerations which in solution are indistinguishable and intrinsically related to, and dependent upon, the dissociative water exchange rate. This realization leads to the broader understanding that a solution state structure can only be appreciated with reference to the dynamics of the system.Keywords
This publication has 44 references indexed in Scilit:
- Picture of a chelate in exchange: the crystal structure of NaHoDOTMA, a ‘semi’-hydrated chelateChemical Communications, 2013
- Lower Ligand Denticity Leading to Improved Thermodynamic and Kinetic Stability of the Gd3+ Complex: The Strange Case of OBETAChemistry – A European Journal, 2012
- Analysis of the Conformational Behavior and Stability of the SAP and TSAP Isomers of Lanthanide(III) NB-DOTA-Type ChelatesInorganic Chemistry, 2011
- Properties, Solution State Behavior, and Crystal Structures of Chelates of DOTMAInorganic Chemistry, 2011
- Water Exchange of a ProHance MRI Contrast Agent: Isomer-Dependent Free-Energy Landscapes and MechanismsInorganic Chemistry, 2011
- Synthesis and Physicochemical Characterization of New C-Functionalized Derivatives of the Gadolinium(III) Complex with 3,6,10-Tris(carboxymethyl)-3,6,10-triazadodecanedioic Acid (H5ttda) Exhibiting Fast Water Exchange – Potential Paramagnetic Reporters for Molecular ImagingHelvetica Chimica Acta, 2007
- Structural and Chiroptical Properties of the Two Coordination Isomers of YbDOTA-Type ComplexesInorganic Chemistry, 2005
- Non-radiative deactivation of the excited states of europium, terbium and ytterbium complexes by proximate energy-matched OH, NH and CH oscillators: an improved luminescence method for establishing solution hydration statesJournal of the Chemical Society, Perkin Transactions 2, 1999
- Structural and Dynamic Parameters Obtained from 17O NMR, EPR, and NMRD Studies of Monomeric and Dimeric Gd3+ Complexes of Interest in Magnetic Resonance Imaging: An Integrated and Theoretically Self-Consistent Approach1Journal of the American Chemical Society, 1996
- Ambiguities in the interpretation of proton magnetic relaxation data in water solutions of Gd3+ ionsThe Journal of Chemical Physics, 1975