Journal of Applied Spectroscopy, Vol. 70, No.

3, 2003

INFLUENCE OF THE TYPE OF A LIGAND ON THE INTENSITY OF LUMINESCENCE OF Ln3+ IONS IN AQUEOUS SOLUTIONS
I. V. Barsukov,a E. N Kabaeva,a V. V. Sytko,a* and S. D. Umreikob UDC 546.27

The luminescence characteristics of hydrated Ln3+ ions and their complexes with some acidic ligands have been investigated. The possibility of determining the stability of the complexes of lanthanides in solutions from the intensity of luminescence bands is shown. The influence of the characteristic features of the f-electron shell of Ln3+ on the formation of the spectrochemical series is discussed. Keywords: luminescence, complexing, three-valent ions of lanthanides, acidic ligands, aqueous solutions. Introduction. As is known (see, e.g., [1, 2]), during the formation of complexes of lanthanides the oscillator strengths of the ff transitions increase compared to those of "free" ions. Here, their value is determined by both the type of ligand environment and the symmetry of coordination polyhedron Ln3+. This made it possible, in particular in [3], to evaluate the stability constants of lanthanide complexes in solutions from the extinction coefficients of supersensitive transitions. In [4], the possibility of applying luminescence to investigate the effects of coordination of Ln3+ ions in solutions was noted. At the same time, luminescent methods have been successfully used to study the effects of ligand substitution in uranium complexes [5, 6]. In the present work, we consider the possibility of applying a luminescent analysis to studying the effects of complexing of Ln3+ in solutions. We investigated the luminescence spectra of hydrated ions Sm3+(4f 5), Eu3+(4f 6), Gd3+(4f 7), Tb3+(4f 8), Dy3+(4f 9), and Tm3+(4f 12) and of their complexes with acidic ligands (F, Cl, Br, I, SO2 4 , 2 3 3+ NO , CO3 , HCOO , and CH3COO ). The concentration of the Ln ions in a solution was 0.001 M. The analysis was based on the integral intensity of the Ln3+ luminescence bands. The spectra were recorded on DFS12-based automated spectrofluorimeters in the 30,000100,000 cm1 range with allowance for the spectral sensitivity of the instruments. 3+ Results and Discussion. Usually, trivalent Ln ions in salts and impurity crystals possess narrow lines of luminescence, which is associated with electron transitions within the limits of the 4f q configuration. In aqueous solutions, luminescence is generally observed only for ions of a lanthanide series beginning with Sm3+, with the Stark structure of the bands of electron transitions being practically not expressed. On excitation in the region of more than 32,000 cm1, the 2G5 2 6HJ transitions are observed in the luminescence spectrum of hydrated Sm3+ and its complexes. The luminescence of Eu3+ is associated with transitions from the 5D0 and 5D1 levels to the 7FJ multiplet levels. For the hydrated Gd3+ and solutions of its complexes a wide band corresponding to the transition from the 6P7 2 level to the ground 8S7 2 state is characteristic; there is also a weak band associated with the 6P5 2 8S7 2 transition. The structure of the luminescence spectrum of Tb3+ is attributable to the 5D4 7FJ transitions, while that of Dy3+, to the 7F9 2 (6HJ, 6FJ) transitions. In analyzing the luminescence of Tm3+, we considered only the 1G4 3H6 transition. Usually, the formation of the Ln3+ complexes in solutions leads to a small bathochromic shift of the bands of electron transitions, an increase in their intensity, and a change in the lifetime of luminescent states, with the greatest
*

To whom correspondence should be addressed.

a

F. Sk or ina Go mel State Univ er sity, 1 04 So vetskaya Str ., Go mel, 24 66 99, Belarus; e-mail: sytko@gsu.unibel.by; bBelarusian State University, Minsk, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 70, No. 3, pp. 417420, MayJune, 2003. Original article submitted October 25, 2002. 470 0021-9037/03/7003-0470$25.00 2003 Plenum Publishing Corporation

TABLE 1. Intensity (rel. units) of the Transitions of the Hydrated Ln3+ Ions and Aqueous Solutions of Their Carbonate Complexes
Type of transition
4 4 4

Hydrated ion 11 125 24 Eu3+ 16 10 13 Gd3+ 103 Tb3+ 38 126 29 11 Dy3+ 76 72 1 Tm3+ 580

Carbonate complex 205 720 1000 111 1000 20 89 1000 471 1000 74 11 325 1000 42 11 1000

G5/2 H5/2
6

G5/2 6H7/2 G5/2 H9/2

6 5

D0 7F1 D0 7F2 D0 7F3 D0 7F4

5 5 5

P7/2 8S7/2
5

D4 7F6 D4 F5
7

5 5 5

D4 7F4 D0 F3
7

4 4 4

F9/2 6H15/2 F9/2 H13/2

6

F9/2 6H11/2 F9/2 H9/2

6 1

G4 H6
3

increase in the intensity occurring in the so-called supersensitive electron transitions. The bands are broadened, but the Stark structure of transitions is not manifested in the luminescence spectra of the Ln3+ complexes in solutions. The changes in the integral intensity of the luminescence bands of the indicated complexes during the formation of the strongest luminescent carbonate Ln(CO3)5 4 complexes are presented in Table 1. These kinds of changes in the luminescence spectra are also observed in complexing with other ligands (see Table 2). It should be noted that such halo gen-anions as Cl , Br , and I form rather weak complexes with Ln3+ in aqueous solutions, whereas fluoride complexes are much more stable. In describing empirically the influence of auxochromic groups (ligands) on the spectroscopic properties of complexes, the so-called spectrochemical series are used [7]. The sequence of ligands in the series is due to the effects of the spin-orbit and electrostatic interaction and reflects the strength of the complex and the substitute capability of the ligand. Various complexing agents have their own spectrochemical series. In particular, for the hexacoordinated Co3+ complexes this series has the form I < Br < Cl < F < CO3 < C2O4 < OH < CH3COO < HCOO < SO4 < NO
2 2 2 3

< H2O .

(1)

The formation of the Ln3+ complexes with ligands Ligx in aqueous solutions can be represented in the form of ligand substitution according to the type Ln(H2O)n + Lig(d) [LnLig(d)(H2O)nd]
3x

(2)

471

TABLE 2. Intensity (rel. units) of the Transitions of the Eu3+ Complexes with Certain Acidoligands
Ligand I (H2O) Br Cl F
5

D0 7F1 50 156 159 160 161

D0 7F2 15 36 42 42 42

Ligand
SO2 4 3

D0 7F1 166 175 178 178 170

D0 7F2 124 135 297 580 1000

NO CH3COO HCOO
CO2 3

where d is dentateness of the ligand. The observed value of the oscillator strength F (integral band intensity) of the electron transition is determined by a sum of the oscillator strengths FLn(H2O) and FLn(Lig) of the electron transitions of the equilibrium system components: F= [Ln(H2O)] [Ln(Lig)] FLn(H O) + FLn(Lig) . 2 cLn cLn (3)

If the luminescence intensity of Ln3+ is considered as a characteristic of the complex strength, then for Eu3+ the corresponding series of acidoligands (investigated in the present work) is as follows: I < H2O < Br < Cl < F < SO4 < NO
2 3

< HCOO < CH3COO < CO3 .

(4)

We note that though the intensity of magnetic dipole transitions is relatively independent of the type of ligand environment (except for iodine), the intensity of electric dipole transitions is sensitive enough to the chemical nature of the ligand. It follows from Table 2 that for halogens complexing is virtually identical, while in series (4) they are arranged in conformity with the values of the total luminescence intensity. In series (4), iodine, according to its displacing capability, precedes water, and this finds its own independent experimental confirmation: aqueous solutions of the EuI3-type complexes are relatively stable only at temperatures <285 K. The high strength of the Eu3+ complexes with CH3COO, HCOO, and CO2 3 can be due to the bidentate character of bonds between the given ligands and a central atom. This fact is supported, in particular, by studies of the laws governing the coordination of the LnLign complexes in solutions [8]. The values of the intensity of the supersensitive transition I(5D0 7F2) in nitrate complexes allow the assumption that the NO3 groups in aqueous solutions, just as halogen-anions, are bonded to europium in a monodentate fashion. + The same laws are also typical of the other Ln3+ complexes, investigated except for Gd3 . For gadolinium, in particular, we failed to stabilize the complexes with iodine (control measurements were performed by absorption spectra according to the procedure given in [3]), whereas the luminescence of the aqueous solutions of the nitrate complexes was virtually completely suppressed. Moreover, analysis of the change in the intensity of the supersensitive transition 6P7 2 8S7 2 of Gd3+ in the luminescence spectrum (Table 3) points to a rather weak complexing with other halogen-anions. The corresponding series of ligands for Gd3+ can be represented in the form NO
3

< Br < Cl < F < H2O < SO4 < CH3COO < HCOO < CO3 .

(5)

This "anomalous" behavior of the Gd3+ complexes can be explained in a quite clear way by taking into account the possibility of participation of the 4f electrons of the Ln3+ ions in the formation of coordination bonds. For the Ln3+ ions the spin-orbital interaction of the 4f electrons is considerably smaller than their electrostatic interaction. In the first RussellSaunders approximation (on neglect of the spin-orbital interaction), the energy of the (4f4f) term is determined by total orbital and spin moments, whereas in the Slater representation, by the radial overk lap integrals F (4f4f), where k = 2, 4, and 6. It should be taken into consideration that typical of the Ln3+ ions is the electron-acceptor role in the formation of chemical bonds and that the atomic 4f orbitals contract more rapidly than

472

TABLE 3. Intensity (rel. units) of the Transitions of the Gd3+ Complexes with Certain Acidoligands
Ligand NO3 Br F
6

P7/2 8S7/2 1 22 22 29 33

Ligand
SO2 4

P7/2 8S7/2 38 53 57 100

Cl

HCOO CH3COO
CO2 3

(H2O)

the distances between the Ln3+ ions and the ligands decrease. Then the integrals of the overlapping of the atomic 4f orbitals of Ln3+ with the orbitals of the ligands must decrease in the series Ce3+ Lu3+ [9, 10]. Allowance for the spin-orbital interaction leads to the removal of degeneration and to the splitting of the basic term (determined by the S+ total mechanical moment J) into the multiplets 2 1LJ. Thus, the LS splitting observed in the spectra reflects the combined effect of the orbital interactions occurring in the Ln3+ ion due to magnetic interactions of the 4f electrons. Stabilization of the electron states of the 4f electron system of Ln3+ corresponds to the decrease in the energy of the S+ barycenter of the 2 1LJ term. Subsequent consideration should be associated with the tendency of the Ln3+ ions to coordinate atoms (and atomic groups) of the immediate neighborhood, which leads to the formation of a complex. In this case, the appearing ligand field (otherwise called a crystal field) causes a further splitting of the 4f term by the Stark mechanism, with the ligand field affecting more considerably the position of the barycenter of the initial electron states. The shift in the position of the energy levels can be considered as a result of screening effects associated with the acceptance of the electron density of the ligands by the Ln3+ ion, which is accompanied by a change not only in the Slater parameters Fk(4f4f) but also in the parameters of the spin-orbital interaction. The additional effect of a decrease in the multiplet energy of the basic terms is imposed on the total lanthanide contraction of the 4f orbital. This effect is nonuniform in the lanthanide series and is equal to zero for La3+ (the initiator of the series), Lu3+ (the last element of the series), and Gd3+ (the middle of the series). Moreover, for the elements of the lanthanide series after Gd3+, paired electrons appear and the exchange-interaction energy decreases. Conclusions. Thus, from the viewpoint of the investigation into the complexing processes and ligand exchange in the solutions of rare-earth compounds, the spectral-luminescent measurements are sufficiently informative. The influence of the chemical nature of the ligand and the symmetry of the coordination polyhedron Ln3+ on the magnitudes of the spin-orbital and electrostatic interactions is manifested in the change of the oscillator strengths of electron transition within the limits of the ff configuration, thus allowing one, by using the integral intensity of the Ln3+ luminescence bands in the complex, to judge the complex strength and the substitute capability of the ligands. In turn, the characteristic features of the f electron shell of Ln3+ have an effect on the complexing processes. In particular, this is reflected in the difference of the spectrochemical series of acidoligands for Gd3+ and of the series for Sm3+, Eu3+, Tb3+, Dy3+, and Tm3+.

REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. R. D. Peacock, Structure and Bonding, 22, 83122 (1976). ktov, L. I. Kononenko, N. P. Efryushkina, and S. V. Beltyukova, Spectrophotometric and LuminesN. S. Polue cence Methods of the Determination of Lanthanides [in Russian], Kiev (1989). I. I. Zheltvai and S. V. Beltyukova, Zh. Neorg. Khim., 43, 15711574 (1998). F. S. Richardson, in: Proc. 15th Rare Earths Res. Conf., Plenum Press, London, (1982), pp. 3536. V. V. Yakshin, N. L. Khokhlova, V. P. Kazakov, and D. D. Afonichev, Radiokhimiya, 26, 4852 (1984). D. L. Clark, S. D. Conradson, R. J. Dodohoe, et al., Inorg. Chem., 33, 14561466 (1999). C. K. Jorgensen, Modern Aspects of Ligand Field Theory, North-Holland, Amsterdam (1971). G. V. Ionova, C. Madic, and R. Guillaumon, Koord. Khim., 27, 471474 (2001). J. D. Axe and G. J. Barns, Phys. Rev., 152, 331340 (1966). G. J. Barns, J. Chem. Phys., 42, 377390 (1965). 473