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Lanthanide Paramagnetic Probes for NMR Spectroscopic Studies of Fast Molecular Conformational Dynamics and Temperature Control. Effective Six-Site Proton Exchange in 18-Crown-6 by Exchange Spectroscopy Full article

Journal Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X
Output data Year: 2012, Volume: 51, Number: 3, Pages: 1427-1433 Pages count : 7 DOI: 10.1021/ic201662q
Authors Babailov Sergey P. 1
Affiliations
1 A. V. Nikolaev’s Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Av. Lavrentyev 3, Novosibirsk, 630090 Russia

Abstract: 1H and 13C NMR measurements are reported for the CDCl3 and CD2Cl2 solutions of [La(18-crown-6)(NO3)3] (I), [Pr(18-crown-6) (NO3)3] (II), [Ce(18-crown-6)(NO3)3] (III), and [Nd(18-crown-6)(NO3)3] (IV) complexes. Temperature dependencies of the 1H NMR spectra of paramagnetic II–IV have been analyzed using the dynamic NMR (DNMR) methods for six-site exchange. Two types of conformational dynamic processes were identified (the first one is conditioned by interconversion of complex enantiomeric forms and pseudorotation of a macrocycle molecule upon the C2 symmetry axis; the second one is conditioned by macrocycle molecule inversion). Application of exchange spectroscopy (2D-EXSY) of DNMR for investigation of this dynamic system (II–IV) simplifies the assignment of the NMR signals and represents the first experimental study of multisite exchange. In the present work, the methodology of paramagnetic 4f (Ce, Pr, and Nd) probe applications for the study of free-energy, enthalpy, and entropy changes in chemical exchange processes, as well as the advantages of this method in a comparison with DNMR studies of diamagnetic substances, is discussed. In particular, as a result of paramagnetic chemical shifts in 4f complexes, the range of measurable rate constants expands considerably compared to the analogous range in diamagnetic compounds. Coordination compounds investigated in the paper represent new types of thermometric NMR sensors and lanthanide paramagnetic probes for in situ temperature control in solution.
Cite: Babailov S.P.
Lanthanide Paramagnetic Probes for NMR Spectroscopic Studies of Fast Molecular Conformational Dynamics and Temperature Control. Effective Six-Site Proton Exchange in 18-Crown-6 by Exchange Spectroscopy
Inorganic Chemistry. 2012. V.51. N3. P.1427-1433. DOI: 10.1021/ic201662q WOS Scopus РИНЦ OpenAlex
Dates:
Submitted: Oct 1, 2011
Accepted: Jan 12, 2012
Published online: Jan 12, 2012
Published print: Jan 17, 2012
Identifiers:
Web of science: WOS:000300474700033
Scopus: 2-s2.0-84856762183
Elibrary: 17976492
OpenAlex: W2330966695
Citing:
DB Citing
Scopus 35
OpenAlex 33
Web of science 36
Elibrary 36
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