Babailov, S. P.

Bryleva, Yu. A.

Zapolotsky, E. N.

BSU Digital Library

 99 
CHEMISTRY OF METAL COMPLEXES 
Molecular  structure  and  paramagnetic  properties  of  lantanides  complexes 
with  bisdiisobutil  dithiophosphinate  and  1,10-phenanthroline  using  NMR 
S. P. Babailov, E. N. Zapolotsky, Yu. A. Bryleva 
A. V. Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia, 
 e-mail babajlov@niic.nsc.r 
Magnetic Resonance Imaging (MRI) is routinely used in the clinic to visualize the structure 
and function of organs. For several applications, including tumor and cardiovascular imaging in 
clinic and in vivo studies, an enhancement in contrast is an absolute requirement to improve the 
sensitivity and the diagnostic contents of the images. For this, several contrast agents (CAs) have 
been developed over the past years, most of which incorporate paramagnetic gadolinium ions 
(Gd3+). Currently, complexes of different lanthanides (Ln, other than Gd), remain largely 
unexplored as probes for nuclear magnetic resonance spectroscopy (NMR) and MRI.   
The features of the molecular structure and paramagnetic properties of Ln complexes with 
the dithiophosphinate R2PS

2
 (R = i-Bu) and 1,10-phenanthroline ligands [Ln(1,10-Phen)((i-
Bu)2PS2)2(NO3)] {where Ln = Nd
3+ (I), Eu3+ (II), Dy3+ (III), Yb3+ (IV) and Lu3+ (V)} in CDCl3 
have been studied by 1H NMR techniques. These complexes are of interest due to the prospect of 
using some of them as fluorescent sensors for biology and medicine. They are also considered as 
potential NMR thermometric probes (see our approach in [1, 2]). The structure of complexes was 
studied in detail by three independent 1H NMR techniques that are analysis of lanthanide-
induced shift (LIS) magnitudes, method of the separation of Fermi-contact and pseudo-contact 
contributions of LIS [3], and calculation of paramagnetic lanthanide-induced relaxation rate 
enhancements [2]. The structure results obtained for these paramagnetic complexes by relaxation 
spectroscopy (RS) of NMR and LIS analysis in solution are mutually consistent with the results 
found for model complex of yttrium by X-ray analysis in the crystalline phase. Paramagnetic 
complexes (I–IV) investigated in this work represent a new type of thermometric NMR sensors 
and lanthanide paramagnetic probes for in situ temperature control in solution. The report also 
contains: (1) comparison of the results obtained and those found for other Ln complexes; (2) the 
information about the molecular structure and the dynamics of related Ln coordination 
compounds with crown-ethers, (EDTA-like) ligands and DOTA-like molecules in solutions. 
 
References 
1. S.P. Babailov. Inorg. Chem. (2012) 51 (3): 1427. 
2. S.P. Babailov. Progr. Nucl. Magnet. Reson. Spectrosc. (2008) 52 (1): 1. 
3. C.N. Reilley, B.W. Good, R.D. Allendoerfer. Anal. Chem. (1976) 48 (11): 1446. 
 


Molecular structure and paramagnetic properties of lantanides complexes  with bisdiisobutil dithiophosphinate and 1,10-phenanthroline using NMR

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Molecular structure and paramagnetic properties of lantanides complexes with bisdiisobutil dithiophosphinate and 1,10-phenanthroline using NMR

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