Polyhedron 20 (2001) 2385– 2391

www.elsevier.com/locate/poly

Study of new lanthanide complexes of 2,6-pyridinedicarboxylate:

synthesis, crystal structure of Ln(Hdipic)(dipic) with Ln= Eu, Gd,
Tb, Dy, Ho, Er, Yb, luminescence properties of Eu(Hdipic)(dipic)
A. Fernandes, J. Jaud, J. Dexpert-Ghys, C. Brouca-Cabarrecq *
Centre d’Elaboration de Matériaux et d’Etudes Structurales du CNRS, 29 rue Jeanne Mar6ig, BP 43 47, 31055 Toulouse Cedex 4, France

Received 7 February 2001; accepted 30 April 2001

Abstract

This paper presents the hydrothermal synthesis of a series of new isomorphous bis-dipicolinato lanthanide complexes:
Ln(Hdipic)(dipic) with Ln = Eu, Gd, Tb, Dy, Ho, Er, Yb, and dipic = 2,6-pyridinedicarboxylate. A structural study has been
realised for the Ho3 + complex. It crystallises in a two-dimensional network, where sheets are parallel to the (100) plane. The
luminescent properties of the analogous Eu3 + complex have been investigated. The composition of the 7FJ levels is consistent with
a true C1 local symmetry: six oxygen and two nitrogen atoms forming a distorted square antiprism. The 5D0 emission lifetime is
only slightly shorter than in [Eu(dipic)3]3 − in solution, but the ligand to metal energy transfer is much less efficient. © 2001
Elsevier Science Ltd. All rights reserved.

Keywords: Rare earth complexes; Dipicolinic acid; Crystal structures; Luminescence

1. Introduction of Ho(Hdipic)(dipic) and luminescent behaviour of the

In this paper, a series of bis-dipicolinato complexes
Ln(Hdipic)(dipic) with Ln=Eu,…,Yb, is described.
These complexes were isolated and investigated during
the course of a more general study of the synthesis and
characterisation of host – guest materials in which a
luminescent lanthanide complex is inserted in an inor-
ganic network [1]. The dipic ligand was chosen because
it is well known to enhance the lanthanides lumines-
cence by a ligand to metal energy transfer mechanism;
for instance, the Eu3 + and Tb3 + tris-dipicolinato com-
plexes are strong emitters in solution [2].
So, we present in this paper the complexes
Ln(Hdipic)(dipic) with Ln=Eu, Gd, Tb, Dy, Ho, Er,
Yb. To our knowledge, very few bis(dipicolinato) lan-
thanide complexes have been investigated by X-ray
diffraction [3–6]. We report the syntheses realised un-
der hydrothermal conditions, the X-ray structural study
* Corresponding author. Tel.: + 33-5-6225-7839; fax: +33-5-6225-
7999.
E-mail address: brouca@cemes.fr (C. Brouca-Cabarrecq).
Eu3 + complex.
2. Experimental
2.1. Synthesis
The syntheses were performed under hydrothermal
conditions. A mixture was prepared of Ln(NO3)3·H2O
(Ln = Eu, Gd, Tb, Dy, Ho, Er, Yb) (1 mmol), H2dipic
(2 mmol), en, 2HCl (2 mmol) and water (10 ml). After
3 days at 150 °C, under autogenous pressure in an
autoclave, the mixture was filtered off, washed with
water and air-dried. The pH was equal to 1.5 –2. Addi-
tion of ethylenediamine to the starting solution proved
to be necessary for the obtention of the pure phase.
There was nevertheless no trace of this compound in
the resulting crystals. Elemental analysis agree rather
well with those calculated from the formula of Ln(-
Hdipic)(dipic) (Table 1).
A reference solution of [1Eu/3H2dipic] was prepared
by dissolving Eu(NO3)3·6H2O (0.1 mmol) and H2(dipic)
(0.3 mmol) in 20 ml of water. The pH was adjusted to

0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 1 ) 0 0 8 4 1 - 5
2386 A. Fernandes et al. / Polyhedron 20 (2001) 2385–2391
approximately 7 with diluted NaOH. This mother
solution was then diluted in water up to 4×10 − 5
mol l − 1.
2.2. Characterisation
IR spectra were recorded between 4000 and 400
cm − 1 on a Perkin – Elmer 1725X FTIR apparatus.
Samples were run as KBr pellets.
The Eu3 + luminescence spectra were recorded with a
Dilor XY dispersive spectrometer equipped with a
Thomson 1024 CCD detector. The optical set-up is
made of an optical microscope. In this configuration,
the volume investigated is about 1 mm3. The excitation
source is a krypton – argon ion laser, the 488 nm line
was selected. This excitation level is situated above the
5
D1 energy level of Eu3 + , emissions from 5D1 and from
5
D0 towards the ground 7F mutiplet can then be ob-
served. The spectral resolution of the set-up is about 30
cm − 1 (0.6 nm). The luminescence was also investigated
with a Perkin –Elmer LS50B spectrofluorimeter operat-
ing in time-resolved mode, equipped with a Hamamatsu
R928 photomultiplier tube. Excitation and emission
bandpasses of 10 nm were used and the excitation
spectra were corrected. The 5D0 emission lifetimes were
measured monitoring the emission intensity at 615 nm
and averaged over at least five separate measurements.
The program calculates an average lifetime assuming a
single exponential decay. The time gates and delays are
adjusted in order to measure an initial intensity I0
slightly below the saturation range and a final intensity
equal to I0/10. The numerical values are given within
9 10%.
X-ray powder diffraction measurements were
recorded on a Seifert diffractometer using Cu Ka radia-
tion. The diffraction pattern for Ho(Hdipic)(dipic) was
Table 1
Elemental analysis (%) for Ln(Hdipic)(dipic) with Ln = Eu, Gd, Tb, Dy, Ho, Er, Yb
Eu(Hdipic)(dipic)
Gd(Hdipic)(dipic)
Tb(Hdipic)(dipic)
Dy(Hdipic)(dipic)
Ho(Hdipic)(dipic)
Er(Hdipic)(dipic)
Yb(Hdipic)(dipic)
a
Elemental analyses were carried out by the ‘Laboratoire Central de Microanalyse du CNRS’ and results are given with an experimental error
equal to about 2% for metals.
calculated using the LAZY PULVERIX program [7].
The diffraction data were collected using an Enraf
Kappa-CCD automatic X-ray single crystal diffrac-
tometer. This goniometer is equipped with a planar
area detector allowing a quick measurement of the
whole diffraction sphere. The structure solution was
found using DIRDIF [8] and refined using the least-
squared methods included in MAXUS [9]. Except for the
hydrogen atoms which were only introduced in the
refinement after their localisation using a difference
Fourier map, all of the others atoms were refined
anisotropically. According to the small value of the
absorption coefficient (5.96 mm − 1) and the regular
shape of the crystal (nearly a small cube of 0.2 mm
edge), after applying a spherical absorption correction,
the final R value dropped to 0.023.
3. Results and discussion
The X-ray diffraction powder pattern of each com-
pound of the series is given in Fig. 1. According to
X-ray powder diffraction, we obtain pure products and
complexes of the type Ln(Hdipic)(dipic) with Ln=Eu,
Gd, Tb, Dy, Ho, Er, Yb which are isostructural. The
formula, Ln(Hdipic)(dipic), is deduced from the struc-
tural determination of a single crystal containing Ho,
representative of this series. The pattern calculated
from the single crystal structure described hereafter is in
good agreement with the observed one.
3.1. Description of the crystal structure of
Ho(Hdipic)(dipic)
Crystal data, intensity measurements and structure
refinements are summarised in Table 2. Selected bond
angles and distances are listed in Table 3.
observed a: Eu, 29.06; C, 35.02; N, 5.76; H, 1.46%
calculated: Eu, 31.47; C, 35.02; N, 5.76; H, 1.46%
observed a: Gd, 31.56; C, 34.52; N, 5.72; H, 1.43%
calculated: Gd, 32.17; C, 34.43; N, 5.74; H, 1.43%
observed a: Tb, 31.89; C, 34.13; N, 5.68; H, 1.43%
calculated: Tb, 32.45; C, 34.28; N, 5.71; H, 1.43%
observed a: Dy, 31.71; C, 33.88; N, 5.56; H, 1.42%
calculated: Dy, 32.92; C, 34.29; N, 5.67; H, 1.42%
observed a: Ho, 31.76; C, 33.90; N, 5.58; H, 1.44%
calculated: Ho, 33.27; C, 34.04; N, 5.64; H, 1.41%
observed a: Er, 31.43; C, 33.70; N, 5.59; H, 1.38%
calculated: Er, 33.53; C, 33.73; N, 5.62; H, 1.41%
observed a: Yb, 33.95; C, 33.32; N, 5.58; H, 1.33%
calculated: Yb, 34.32; C, 33.33; N, 5.56; H, 1.39%
 A. Fernandes et al. / Polyhedron 20 (2001) 2385–2391 2387

O(1)O(2)O(3)O(4) and dipic2= N(2)C(8)C(9)

C(10)C(11)C(12)C(13)C(14)O(5)O(6)O(7)O(8),
then the environment of the holmium cation will be
described and lastly the crystalline structure.
Dipic1 and dipic2 act as tridentate ligands towards
the Ho3 + cation, with a pyridine nitrogen atom and
two carboxylic oxygen atoms, (N(1), O(1), O(3)) and
(N(2), O(5), O(7)), respectively (Fig. 2). Moreover,
dipic2 acts as a bis-monodentate ligand with two car-
boxylic oxygen atoms O(6) and O(8) (towards HoV and
HoIV, respectively). Only the oxygen atoms O(2) and
O(4) of dipic1 are not coordinated. One dipic anion is
dianionic (dipic2), the other one (dipic1) must be
monoprotonated to maintain electroneutrality. The
proton was unambiguously located near O(1), from a
difference Fourier synthesis. It is rather uncommon that
the proton is located near an oxygen atom coordinated
to the metal cation. As a consequence, the C(1)O(1)
bond differs considerably from the other CO bonds, it
is by far the longest one (1.3442(3) A, ) (Table 3).
Shorter bond lengths indicate conjugation of the double
Fig. 1. Powder patterns of the series Ln(Hdipic)(dipic) with Ln =Eu, bond after deprotonation. Closer examination of the
Gd, Tb, Dy, Ho, Er, Yb. CO bond lengths reveals that C(1)O(2) and
C(7)O(4) are the shortest ones, probably because O(2)
Table 2 and O(4) are not coordinated. Considering the whole
Crystal data, data collection and structure refinement for ligands, dipic1 is nearly planar, the maximum deviation
Ho(Hdipic)(dipic)
from planarity is 0.0834(2) A, for O(3), on the other
Empirical formula Ho(C7NO4H4)(C7NO4H3) hand, dipic2 shows significant deviation from planarity
Colour/shape colourless/cubic with atom distances to the mean plane reaching −
Formula weight (g mol−1) 496.146 0.4442(2) A, for O(8).
Space group P21/c The eight coordination (Table 3) of the holmium
Temperature (K) 298
Unit cell dimensions
cation corresponds to a distorted square antiprism. The
a (A, ) 12.1997(1) dihedral angle between the bases (O(3), O(5), O(8I),
b (A, ) 8.3710(1) N(2)) and (O(1), O(6II), O(7), N(1)) is equal to 3.45°.
c (A, ) 13.4279(2) This coordination number must be underlined because
i (°) 102.3782(6)
in most of the cases, lanthanide 2,6-pyridinedicarboxy-
V (A, 3) 1339.43(2)
Z 4
late complexes exhibit a nine coordination around the
zcalc (g cm−3) 2.460 lanthanide cation. For example, in bis-dipicolinato
v(Mo Ka) (mm−1) 5.96 complexes, two ligands are tridentate and three bonds
Wavelength (Mo Ka) (A, ) 0.71073 exist between the lanthanide and water molecules [4], or
Index ranges −225h522, −155k515, two water molecules and the oxygen of a bridging dipic
−245l524
Reflections independent 8389
ligand [3]. The HoN bonds are as usual longer than
Reflections observed 7210 the HoO bonds (Table 3), except for HoO(1) which is
[I\3|(I)] longer than the others. We can consider that H(1) pulls
Structure refinement Maxus O(1) away and so bonds involving O(1) are longer than
Number of refined 227 the others.
parameters
Extinction method Zachariasen
Dipic2 is coordinated to three metallic centres (Ho3 +
Weights w= 1/[| 2(F o2)+0.0300F o2] x, y, z; Ho3 + x, 1/2 − y, 1/2 + z; Ho3 + − x, 1/2 +y,
R 0.023 1/2 − z) giving rise to neutral, unlimited sheets parallel
wR 0.031 to the (100) plane (Fig. 3). Dipic1 is only coordinated
Goodness-of-fit on F 2 1.435 to one metallic centre (Ho3 + x, y, z), and it is situated
in a plane almost perpendicular to the sheets. Indeed,
the dihedral angle between the planes of the two lig-
The asymmetric unit of this new compound is Ho- ands, dipic1 and dipic2, is equal to 101°.
(Hdipic)(dipic). Two ligands will be examined here: Ho(Hdipic)(dipic) has then a polymeric nature, due
dipic1 = N(1)C(1)C(2)C(3)C(4)C(5)C(6)C(7) to the capacity of multiple bonding via the carboxylate
2388 A. Fernandes et al. / Polyhedron 20 (2001) 2385–2391

Table 3
Selected interatomic distances (A, ) and bond angles (°) for Ho(Hdipic)(dipic)

Around Ho
Bond lengths
HoO(8I) 2.2532(1) HoO(7) 2.3958(2)
HoO(6II) 2.3022(1) HoN(2) 2.4606(2)
HoO(3) 2.3168(1) HoN(1) 2.4767(1)
HoO(5) 2.3693(1) HoO(1) 2.5081(1)
Bond angles
O(1)HoO(3) 128.78(1) O(1)HoO(5) 89.77(1) O(1)HoO(7) 77.14(1)
O(1)HoN(1) 62.66(1) O(1)HoN(2) 74.18(1) O(1)HoO(8I) 153.65(1)
O(1)HoO(6II) 91.88(1) O(3)HoO(5) 78.08(1) O(3)HoO(7) 145.73(1)
O(3)HoN(1) 66.15(1) O(3)HoN(2) 136.52(1) O(3)HoO(8I) 77.50(1)
O(3)HoO(6II) 80.33(1) O(5)HoO(7) 129.58(1) O(5)HoN(1) 77.77(1)
O(5)HoN(2) 64.28(1) O(5)HoO(8I) 94.89(1) O(5)HoO(6II) 153.49(1)
O(7)HoN(1) 131.91(1) O(7)HoN(2) 65.29(1) O(7)HoO(8I) 79.97(1)
O(7)HoO(6II) 76.40(1) N(1)HoN(2) 121.70(1) N(1)HoO(8I) 143.64(1)
N(1)HoO(6I) 79.55(1) N(2)HoO(8I) 84.53(1) N(2)HoO(6II) 141.16(1)
O(8I)HoO(6II) 95.28(1)
Dipicolinic acid
Bond lengths
O(1)C(1) 1.3442(3) C(1)C(2) 1.4908(3) O(5)C(8) 1.2572(2)
O(2)C(1) 1.2024(3) C(2)C(3) 1.3818(3) O(6)C(8) 1.2556(2)
O(3)C(7) 1.2584(2) C(3)C(4) 1.3895(3) O(7)C(14) 1.2521(2)
O(4)C(7) 1.2388(3) C(4)C(5) 1.3878(3) O(8)C(14) 1.2590(2)
N(1)C(2) 1.3380(2) C(5)C(6) 1.3902(3) N(2)C(9) 1.3409(2)
N(1)C(6) 1.3448(2) C(6)C(7) 1.5125(3) N(2)C(13) 1.3343(2)
C(8)C(9) 1.5129(2) C(3)H(C3) 0.9558(2) C(10)H(C10) 0.9744(2)
C(9)C(10) 1.3847(2) C(4)H(C4) 0.9600(2) C(11)H(C11) 0.9565(2)
C(10)C(11) 1.3948(3) C(5)H(C5) 0.9636(2) C(12)H(C12) 0.9695(2)
C(11)C(12) 1.3903(2) C(1)H(O1) 1.0400(2)
C(12)C(13) 1.3889(2)
C(13)C(14) 1.5038(2)
Hydrogen bonds
Bond lengths
O(1)···O(4VI) 2.5129(1)
O(3)···O(6II) 2.9792(2)
O(3)···O(8I) 2.8609(2)
O(6)···O(7V) 2.9061(2)
O(6)···N(1V) 3.0602(1)
O(7)···O(8I) 2.9892(2)

Symmetry codes: (I) −x, y−1/2, −z+1/2; (II) x, −y+1/2, z−1/2; (V) x, −y+1/2, z+1/2; (VI) x, y+1, z.

groups. The peculiarity of the compound described here
is that it crystallises without any water molecules, which
is supposed to favour good luminescent properties.
Hydrothermal synthesis is a good choice to reach this
aim. In previous works realised in our research group,
this fact was already observed. Indeed, a systematic
study of lanthanide squarates confirmed that complexes
prepared under hydrothermal conditions crystallise
with less water molecules [10]. A search in the Cam-
bridge Data Base [11] reveals that only one dipic com-
plex crystallises without water molecules: (N(CH3)4)2-
[La(Hdipic)2(dipic)]Cl [12]. To our knowledge Ho(-
Hdipic)(dipic) is the second one. Comparing it with the
corresponding hydrated bis-dipicolinato complex
[La(Hdipic)(dipic)(H2O)2]·4H2O [3], it may be noticed
that polymeric chains extending along the c-axis occur
in the hydrated lanthanum compound, whereas sheets
parallel to the (100) plane constitute the network of the
anhydrous holmium compound.
3.2. IR absorption
Most of the features observed in the IR absorption
spectrum are almost identical to those of
Ca(dipic)·3(H2O) and (H2dipic) [13]. Bands due to the
vibrations in the pyridine rings are almost unchanged in
the various compounds. By analogy with the calcium
salt, bands at (1609, 1633 cm − 1) and (1407, 1395
cm − 1) are assigned to the antisymmetrical and symmet-
rical stretching of the carboxylate groups O(5)
C(8)O(6), O(7)C(14)O(8), and O(3)C(7)O(4). A
well-defined band is observed at 1745 cm − 1. This vibra-
tion energy is characteristic of double bonding and it is
assigned to the C(1)O(2) stretching. Indeed, this bond
 A. Fernandes et al. / Polyhedron 20 (2001) 2385–2391 2389

made by six oxygen atoms forming a trigonal prism

with three nitrogen atoms capping the faces [14]. The
ideal symmetry in [Eu(dipic)3]3 − is D3h, allowing 0, 2, 1
and 3 lines for the 5D0 “ 7F0,1,2 and 4 transitions, respec-
tively, which is very consistent with the observations
(Fig. 4). The 5D0 “ 7F3 emission, weak and of mixed
(electric dipolar+magnetic dipolar) character, is not
considered. The spectra observed for the compounds
[Eu(dipic)3][N(C2H5)4]3·9H2O [15] and [Eu(dipic)3]Na3
[16] exhibit similar features, assigned to very weak
distortions with respect to the D3 point symmetry: 0, 2,
2 and 4 lines allowed in D3 symmetry for the above-
mentioned transitions. In these three examples, the

Fig. 2. ORTEP view of the Ho(Hdipic)(dipic) complex, showing 50%

probability displacement ellipsoids. H atoms are omitted for clarity.
Symmetry codes are: (I) − x, y−1/2, − z+ 1/2; (II) x, − y +1/2,
z −1/2; (III) −x, −y, − z; (IV) − x, y+1/2, −z + 1/2; (V) x,
− y+ 1/2, z+ 1/2.

Fig. 3. View of a layer parallel to (100) plane. Symmetry codes are as

reported in Fig. 2.

length (1.2024(3) A, ) is that of a double bond. Supple-

mentary bands are also seen at 1362, 1307 and 1290
cm − 1 and are tentatively assigned, at least for a part of
them, to the C(1)O(1) stretching.

3.3. Luminescent properties

The bottom part of Fig. 4 displays the emission

spectrum of Eu(Hdipic)(dipic) microcrystals together
with that of a solution [1Eu/3H2dipic], 4×10 − 5
mol l − 1 in water, pH7. This solution is considered
Fig. 4. Eu3 + emission and excitation spectra recorded on
here as a reference for the [Eu(dipic)3]3 − assembly, it Eu(Hdipic)(dipic) microcrystals and [1Eu/3dipic] 4 ×10 − 5mol l − 1 in
has been well established that at this pH the complexa- water. Top: excitation, monitoring wavelength 615 nm, bottom:
tion is complete and the Eu3 + coordination sphere is emission, excitation wavelength 275 nm.
2390 A. Fernandes et al. / Polyhedron 20 (2001) 2385–2391
Fig. 5. High resolution emission spectrum recorded on a
Eu(Hdipic)(dipic) monocrystal, excitation wavenumber 20492 cm − 1.
Eu3 + emission spectra actually reflect a third-order
symmetry axis at the metal site. Eu(Hdipic)(dipic) on
the contrary exhibits a rather intense 5D0 “ 7F0 line,
followed by three well split 5D0 “ 7F1 components.
The Eu3 + emission spectrum observed on a single
crystal with the Dilor set-up (see Section 2) is displayed
in Fig. 5. Although the excitation energy is situated
slightly above 5D1, only the emission from 5D0 is ob-
served. The uniqueness of the 5D0 “ 7F0 line is confi-
rmed. Almost all the transitions towards the 7FJ
sublevels can be identified: 1, 3, 5 and 8 lines observed
for 5D0 “ 7F0,1,2 and 4. The sublevels are well isolated and
there is no evidence of a pseudo-symmetry at the Eu3 +
site. These observations are in agreement with the
X-ray diffraction results, Ln3 + is found on a single site
of C1 symmetry. Moreover, as stated above, six oxygen
atoms are directly bonded to the Ln3 + , five of them
(O(5), O(3), O(8), O(6) and O(7)) pertain to carboxylate
groups, whereas O(1) is linked both to the proton and
to the lanthanide, which results in an abnormally long
LnO(1) distance (Table 3), on the other side. There is
no evident symmetry relationship between the two ni-
trogens with respect to Ln. No symmetry (higher than
C(1)) can then be proposed to describe the europium
site.
In Fig. 4 (top) are displayed the Eu3 + fluorescence
excitation spectra of the studied solid complex and of
the [1Eu/3H2dipic] solution. As expected, there is an
effective energy transfer from the ligand towards the
rare earth. Two dipic-associated absorption bands are
observed in the reference solution (at 275 and 220 nm),
whereas one broader feature centred around 250 nm is
observed for the solid. The intensity ratio of the dipic-
associated versus the intra-4f6 (7F0 “ 5L6 at 395 nm)
excitation bands, which gives an evaluation of the
ligand to cation energy transfer efficiency, is about 180
in the solution and only 6.5 in the investigated solid.
The average ratio [ligand]/[Eu] equals 3 in the solution
versus 2 in the solid, which is not enough to explain the
much lower energy transfer observed in this last case,
so that another origin for this difference must be
searched for, for instance in the geometries of the
ligands with respect to the rare earth.
The 5D0 emission lifetime in Eu(Hdipic)(dipic) is
t= 1.359 0.10 ms. The corresponding emission proba-
bility is P= 0.749 0.07 ms − 1. In the [1Eu/3H2dipic]
solution we measured 0.649 0.07 ms − 1 in agreement
with the results given in Ref. [17]. In the reference
solution, the Eu3 + coordination sphere is made by
three nitrogen and six oxygen atoms from totally de-
protonated carboxylate groups. In the solid complex
under consideration, there are two nitrogen and five
oxygen atoms from deprotonated carboxylate groups
and the peculiar oxygen O(1) from the (C(1)O(1)H)
group (see Fig. 1 and the discussion of the structural
determination above). The difference between the two
probabilities DP = 0.10 ms − 1 is weak. It may be inter-
preted in the first approximation as reflecting the
change in the 5D0 non-radiative de-excitation probabil-
ity induced by replacing one carboxylate by one hy-
droxyl in the Eu3 + coordination sphere. It may be
noticed that bonding with the hydroxyl O(1)H group
is a much less efficient 5D0 de-excitation pathway than
is the coupling with H2O molecules. For comparison,
following the consideration of 5D0 emission decays in
Eu –carboxymethoxysuccinate complex solutions, the
value DP = 0.45 ms − 1 was assigned to the replacement
of one bonded carboxylate by one bonding OH from
H2O [18].
In summary, three points may be underlined. The
composition of the 7FJ levels in Eu(Hdipic)(dipic) is
consistent with a symmetry much lower than observed
 A. Fernandes et al. / Polyhedron 20 (2001) 2385–2391
in europium tris-dipicolinato complexes. The 5D0 emis-
sion lifetime is only slightly shorter than that of
[Eu(dipic)3]3 − in solution but the ligand to metal en-
ergy transfer is much less efficient.
4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 150212 for complex
Ho(Hdipic)(dipic). Copies of this information may be
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: + 44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
Acknowledgements
The authors wish to thank R. Sirvin (LPST, UPS,
Toulouse, France) for his technical help and C. Picard
(LSPCMIB, UPS, Toulouse, France) for helpful
discussions.
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