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

Sergey P. Babailov

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21 Citations (Scopus)

Abstract

1H and 13C NMR measurements are reported for the CDCl 3 and CD 2Cl 2 solutions of [La(18-crown-6)(NO 3) 3] (I), [Pr(18-crown-6) (NO 3) 3] (II), [Ce(18-crown-6)(NO 3) 3] (III), and [Nd(18-crown-6)(NO 3) 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 C 2 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.

Original languageEnglish
Pages (from-to)1427-1433
Number of pages7
JournalInorganic Chemistry
Volume51
Issue number3
DOIs
Publication statusPublished - 6 Feb 2012
Externally publishedYes

Fingerprint

dynamic control
Lanthanoid Series Elements
temperature control
Temperature control
Molecular dynamics
Protons
Nuclear magnetic resonance
Spectroscopy
molecular dynamics
nuclear magnetic resonance
protons
probes
spectroscopy
Molecules
Chemical shift
18-crown-6
Free energy
chemical equilibrium
molecules
Enthalpy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

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abstract = "1H and 13C NMR measurements are reported for the CDCl 3 and CD 2Cl 2 solutions of [La(18-crown-6)(NO 3) 3] (I), [Pr(18-crown-6) (NO 3) 3] (II), [Ce(18-crown-6)(NO 3) 3] (III), and [Nd(18-crown-6)(NO 3) 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 C 2 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.",
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N2 - 1H and 13C NMR measurements are reported for the CDCl 3 and CD 2Cl 2 solutions of [La(18-crown-6)(NO 3) 3] (I), [Pr(18-crown-6) (NO 3) 3] (II), [Ce(18-crown-6)(NO 3) 3] (III), and [Nd(18-crown-6)(NO 3) 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 C 2 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.

AB - 1H and 13C NMR measurements are reported for the CDCl 3 and CD 2Cl 2 solutions of [La(18-crown-6)(NO 3) 3] (I), [Pr(18-crown-6) (NO 3) 3] (II), [Ce(18-crown-6)(NO 3) 3] (III), and [Nd(18-crown-6)(NO 3) 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 C 2 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.

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