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Polyhedron 52 (2013) 856865

Contents lists available at SciVerse ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

Synthesis, crystal structure and luminescence of novel Eu3+, Sm3+ and Gd3+
complexes of 1,3,5- and 1,2,4-triazines
Lefkia Panayiotidou a, Marios Stylianou a, Nikos Arabatzis a, Chryssoula Drouza b,, Panagiotis Lianos c,,
Elias Stathatos d,, Anastasios D. Keramidas a,
a

Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus


Department of Agricultural Sciences, Biotechnology and Food Science, Cyprus University of Technology, Lemesos 3603, Cyprus
Electrical Engineering Department, Technological-Educational Institute of Patras, 26334 Patras, Greece
d
Department of Engineering Science, University of Patras, 26500 Patras, Greece
b
c

a r t i c l e

i n f o

Article history:
Available online 20 July 2012
Dedicated to Alfred Werner on the 100th
Anniversary of his Nobel Prize in Chemistry
in 1913.
Keywords:
Europium
Samarium
Gadolinium
Triazine
Crystal structure
Luminescence

a b s t r a c t
New Eu3+, Sm3+ and Gd3+ complexes of triazine ligands 2,4,6-tri(2-pyridyl)-1,3,5-triazine, 3,5,6-tri(2-pyridyl)-1,2,4-triazine and 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine were synthesized. The structure of ve
of them was established by single crystal X-ray crystallography. Various aspects of the triazine ligands
such as steric interactions, deviation from the planarity and coordination mode dene the structure of
the complexes. The 1H NMR spectra of the solutions of Eu3+ and Sm3+ molecules showed broad paramagnetic shifted peaks assigned to the protons of the ligated triazines. The powder EPR spectra of the Gd3+
complexes exhibited a broad peak centered at g = 2. All Eu3+ and Sm3+ complexes display characteristic
lanthanide emission upon UV excitation. The enhancement of the luminescence is attributed to the
effective energy transfer from the triazine ligand to the lanthanide ion. 1,2,4-Triazines show to be better
sensitizers for Eu3+ and Sm3+ than the 1,3,5-triazine ligand. Co-coordination of the triazines with b-diketonate ligands further enhances the luminescence of the lanthanides. This enhancement was attributed to
the synergistic effect of the two ligands and/or the decrease of the vibrational quenching processes.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
The enhancement of the luminescence of lanthanides through
the effective energy transfer from suitable organic ligands ligated
to the metal ions is of great interest because of the numerous applications these materials can nd in optical technologies [1,2]. Besides
the lanthanide elements and the electronic properties of the ligand,
the success of these materials depends on the molecular structure of
the complexes. Some of the aspects, these compounds should be
considered for, include: saturation of the coordination sphere, inhibition of luminescence quenching through vibrational coupling,
high stability and facile device fabrication [3]. The photophysical
properties, thermal and chemical stabilities, and processibility of
these complexes can be modied and ne-tuned by judiciously
chosen ligand combinations.
So far, the most studied complexes satisfying the above considerations are the b-diketonate-lanthanides [4], particularly, neutral
Corresponding authors. Tel.: +357 25002503; fax: +357 25002655 (C. Drouza);
tel.: +30 2610997587; fax: +30 2610997803 (P. Lianos); tel.: +30 2610369242;
fax: +30 2610369193 (E. Stathatos); tel.: +357 22892764; fax: +357 22895454
(A.D. Keramidas).
E-mail addresses: chryssoula.drouza@cut.ac.cy (C. Drouza), lianos@upatras.gr
(P. Lianos), estathatos@teipat.gr (E. Stathatos), akeramid@ucy.ac.cy (A.D. Keramidas).
0277-5387/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.07.029

tris-diketonate complexes containing one or more neutral ligands.


Although the effect of the b-diketonates structure on the
photophysical properties of the lanthanides has been extensively
studied, the dependence on the molecular structure of the neutral
ligand is still unexplored.
The last few years, we have been interested in developing
highly luminescent lanthanide complexes for potential applications in organic light-emitting devices [5,6] and luminescent solar
concentrators [7], particularly, complexes containing azo-heterocyclic pyridyl-triazine ligands. Triazine ligands have been chosen
because complexes of the general formula [Ln(b-diketonate)3(triazine)] signicantly enhance the photoluminescence of the lanthanides [810]. In addition, these complexes exhibit high thermal
stability and volatility; required properties for the deposition of
lms through vacuum evaporation techniques in the manufacture
of organic light-emitting devices.
In this work, we have investigated the structure and the
luminescent properties of the Eu3+, Sm3+ and Gd3+ complexes of
2,4,6-tri(2-pyridyl)-1,3,5-triazine (135-tptz), 3,5,6-tri(2-pyridyl)1,2,4-triazine (124-tptz) and 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine (dptz) (Scheme 1). All Eu3+ and Sm3+ complexes display
characteristic lanthanide emission upon UV excitation. Despite
their similarities, steric effects force azo-heterocycles to form

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865

857

Scheme 1. Drawings and numbering of the azo-heterocyclic ligands used in this work. Red color denotes the ligating to lanthanides atoms. (Color online.)

complexes of various molecular structures, affecting the


photoluminescence intensity of the lanthanides. Replacement of
the Cl or NO3 and solvent co-ligands with two or three 1,1,1-triuoro-2,4-pentanedionate (tfac) ligands enhances even more the
photoluminescence of the lanthanides. The lanthanides luminescent properties related to the structural features of the complexes
are discussed.

2. Experimental
Reagent grade 2-cyanopyridine 99%, hydrazine monohydrate
98%, 2-pyridinecarboxaldehyde 99%, 1,1,1-triuoro-2,4-pentanedione (Htfac) 98%, samarium(III) nitrate hexahydrate 99.9%, europium(III) chloride hexahydrate 99.9%, gadolinium(III) nitrate
hexahydrate 99.9% were purchased from Aldrich. All chemicals
were used without further purication. 2,4,6-tris(2-pyridyl)1,3,5-triazine (135-tptz) [11], 3,5,6-tris(2-pyridyl)-1,2,4-triazine
(124-tptz) [12] and 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine
(dptz) [12] (Scheme 1) were synthesized according to the literature in 56%, 47% and 57% yield respectively. UV spectra were recorded on a Shimadzu UV-1601 Spectrophotometer. Conductivity
measurements were obtained using a Jenway 4020 conductivity
meter.

2.4. [Sm(135-tptz)(NO3)3]3H2O (4)


The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from 2-propanol.
Yield (68%). KM at 298 K in methanol: 23 X1 cm2 mol1. Anal.
Calc. for C18H18N9O12Sm: C, 30.76; H, 2.58; N, 17.44. Found: C,
30.49; H, 2.61; N, 17.21%.
2.5. [Sm(124-tptz)(NO3)3]3H2O (5)
The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from 2-propanol.
Yield (67%). KM at 298 K in methanol: 28 X1 cm2 mol1. Anal. Calc.
for C18H18N9O12Sm: C, 30.76; H, 2.58; N, 17.44. Found: C, 30.51; H,
2.51; N, 17.34%.
2.6. [Sm(dptz)2(NO3)3]CH3CN1.5H2O (6)
The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from acetonitrile.
Yield (67%). KM at 298 K in methanol: 23 X1 cm2 mol1. Anal.
Calc. for C42H31N12O10.5Sm: C, 50.54; H, 3.13; N, 16.84. Found: C,
50.34; H, 3.24; N, 16.83%.
2.7. [Eu(135-tptz)(acacF3)2(CH3OH)2]Cl (7)

2.1. [Eu(135-tptz)Cl2(CH3OH)3]Cl (1)


A methanolic solution (10 mL) of 135-tptz (0.50 g, 1.6 mmol)
and EuCl36H2O (0.57 g, 1.6 mmol) were stirred overnight at
40 C. Ether was added into the solution until a pale pink solid
was precipitated which was isolated by ltration. The solid was
recrystallized from 2-propanol and dried in vacuum yielding
0.74 g, (70%). KM at 298 K in methanol: 118 X1 cm2 mol1. Anal.
Calc. for C21H24Cl3N6O3Eu: C, 37.83; H, 3.63; N, 12.60. Found: C,
37.73; H, 3.78; N, 12.55%.

2.2. [Eu(124-tptz)Cl2(CH3OH)3]Cl (2)


The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from 2-propanol.
Yield (70%). KM at 298 K in methanol: 105 X1 cm2 mol1. Anal.
Calc. for C21H24Cl3N6O3Eu: C, 37.83; H, 3.63; N, 12.60. Found: C,
37.69; H, 3.81; N, 12.45%.

A methanolic solution (10 mL) of 1,1,1-triuoro-2,4-pentanedione (0.308 mL, 2.55 mmol) and NaOH (2.55 mL, 1 M aqueous solution) were dropwise added to a methanolic solution (7 mL) of
complex 1 (0.78 g, 0.85 mmol). The resulting solution was stirred
overnight at 40 C. Water was added into the solution resulting in
precipitation of a pale pink solid which was isolated by ltration.
The solid was recrystallized from 2-propanol/nitromethane. The solid was allowed to dry in vacuum to yield 0.36 g, (63%). KM at 298 K
in methanol: 78.6 X1 cm2 mol1. Anal. Calc. for C30H28ClEuF6N6O9:
C, 41.42; H, 3.24; N, 9.66. Found: C, 41.29, H, 3.03, N, 9.51%.
2.8. [Eu(124-tptz)(acacF3)3] (8)
The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from ethanol. Yield
(68%). KM at 298 K in methanol: 18 X1 cm2 mol1. Anal. Calc. for
C33H24F9N6O6Eu: C, 42.92; H, 2.62; N, 9.10. Found: C, 42.24, H,
2.61, N, 9.20%.

2.3. [Eu(dptz)2Cl2(CH3OH)2]Cl (3)

2.9. [Eu(dptz)(acacF3)3] (9)

The synthesis of this compound was performed in a similar


manner as above. The solid was recrystallized from 2-propanol.
Yield (68%). KM at 298 K in methanol: 110 X1 cm2 mol1. Anal.
Calc. for C42H36Cl3N8O2Eu: C, 53.49; H, 3.85; N, 11.88; Found: C,
53.21; H, 3.65; N, 11.72%.

The synthesis of this compound was performed in a similar


manner as above. The solid was recrystallized from 2-propanol.
Yield (67%). KM at 298 K in methanol: 18 X1 cm2 mol1 at
1 mM. Anal. Calc. for C35H26F9N4O6Eu: C, 45.62; H, 2.84; N, 6.08.
Found: C, 45.31, H, 2.85, N, 6.78%.

858

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865

Table 1
Experimental data on X-ray diffraction study of 68 and 10, 11.a,b

Empirical formula
Formula weight
Crystal system
Space group
Unit cell dimensions
a ()
b ()
c ()
a ()
b ()
c ()
Volume (3)
Z, d (g/cm3)
l (mm1)
F(0 0 0)
h Range
Limiting indices

Reections collected/unique
Rint
Data/parameters
Goodness-on-t (GOF) on F2
Final R [I > 2r(I)]
R (all data)
a
b

10

11

C84H56N24O21Sm2
2038.23
triclinic

P1

C30H34ClEuF6N6O9
924.04
triclinic

P1

C33H24EuF9N6O6
923.54
triclinic

P1

C28H20F6N7O7Sm
830.86
triclinic

P1

C33H24F9N6O6Sm
921.93
triclinic

P1

17.2709(13)
17.6617(9)
18.0433(12)
115.389(6)
108.197(6)
100.398(5)
4395.2(5)
2, 1.540
1.409
2040
3.0531.19
24 6 h 6 24
24 6 k 6 24
24 6 l 6 25
86 491/24 873
0.0357
24 873/1404
0.971
R1 = 0.0311
wR2 = 0.0753
R1 = 0.0508
wR2 = 0.0771

9.083
10.068
19.651
85.00
84.61
76.37
1734.8
2, 1.769
1.979
924
3.6031.20
13 6 h 6 13
14 6 k 6 14
28 6 l 6 28
38 551/10 261
0.0331
10 261/552
1.070
R1 = 0.0521
wR2 = 0.1332
R1 = 0.0587
wR2 = 0.1411

9.4649(7)
10.7732(6)
20.1965(14)
80.151(5)
79.250(6)
63.804(7)
1806.2(2)
2, 1.698
1.835
912
3.1030.90
13 6 h 6 13
15 6 k 6 15
27 6 l 6 27
33 044/10 029
0.0240
10 029/540
1.042
R1 = 0.0379
wR2 = 0.1004
R1 = 0.0455
wR2 = 0.1028

8.9137(7)
10.2963(8)
17.8185(15)
82.160(7)
84.260(7)
72.312(7)
1540.5(2)
2, 1.791
2.000
818
3.2331.22
12 6 h 6 12
14 6 k 6 14
25 6 l 6 24
35 367/9082
0.0319
9082/433
1.061
R1 = 0.0454
wR2 = 0.1402
R1 = 0.0549
wR2 = 0.1429

9.4648(6)
10.7766(9)
20.2229(17)
80.139(7)
79.277(6)
63.995(7)
1812.1(2)
2, 1.690
1.719
910
3.1031.07
13 6 h 6 13
15 6 k 6 15
28 6 l 6 28
39 732/10 376
0.0308
10 376/496
1.010
R1 = 0.0376
wR2 = 0.1078
R1 = 0.0499
wR2 = 0.1099

All structures determined at T = 100 K using Mo Ka radiation (k = 0.71073 ).


Renement method, full-matrix least-squares on F2.

2.10. [Sm(135-tptz)(acacF3)2(NO3)] (10)


The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from 2-propanol/
nitromethane. Yield (63%). KM at 298 K in methanol: 23.6
X1 cm2 mol1. Anal. Calc. for C28H20F6N7O7Sm: C, 40.48; H, 2.43;
N, 11.80. Found: C, 40.91, H, 2.54, N, 11.41%.
Scheme 2. Synthetic route of complexes 112.

2.11. [Sm(124-tptz)(acacF3)3]2CH3NO2 (11)


The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from 2-propanol/
nitromethane. Yield (66%). KM at 298 K in methanol: 26
X1 cm2 mol1. Anal. Calc. for C36H30F9N8O10Sm: C, 40.94, H,
2.86, N, 10.61. Found: C, 40.70, H, 2.76, N, 10.35%.
2.12. [Sm(dptz)2(acacF3)3]2H2O (12)
The synthesis of this compound was performed in a similar
manner as above. The solid was recrystallized from acetonitrile.
Yield (65%). KM at 298 K in methanol: 4.61 X1 cm2 mol1. Anal.
Calc. for C55H44F9N8O8Sm: C, 52.17; H, 3.50; N, 8.85. Found: C,
52.15, H, 3.09, N, 8.88%.
2.13. [Gd(135-tptz)(NO3)3]2.5H2O (13) [Gd(124-tptz)(NO3)3)]3H2O
(14) [Gd(dptz)2(NO3)3] (15)

Fig. 1. Ortep drawing (50% of probability) of 6. Hydrogen atoms have been omitted
for clarity.

The syntheses of the Gd3+ complexes were performed in a manner similar to 1. The solids of 13 and 14 were recrystallized from
ethanol and of 15 from acetonitrile. Yield (65%). Anal. Calc. for
(13) C18H17GdN9O11.5: C, 30.86; H, 2.45; N, 17.99%. Found: C,
30.99, H, 2.51, N, 18.11. Anal. Calc. for (14) C18H18GdN9O12: C,
30.47; H, 2.56; N, 17.76. Found: C, 30.49, H, 2.53, N, 17.82%. Anal.
Calc. for (15) C18H18GdN9O12: C, 49.84; H, 2.93; N, 15.98. Found:
C, 49.90, H, 2.77, N, 16.01%.

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865

859

Fig. 2. Ortep drawing (50% of probability) of 7. Hydrogen atoms have been omitted for clarity.

the nal renement details are given in Table 1. The positions of


hydrogen atoms were calculated from stereochemical considerations and kept xed isotropic during renement or found in DF
map and rened with isotropic thermal parameters. Crystals suitable for X-ray diffraction studies were isolated from slow evaporation of an acetonitrile solution of 6 and an ethanol solution of 8,
and from slow diffusion of nitromethane in the 2-propanol solutions of 7, 10 and 11.
2.15. NMR spectroscopy
NMR spectra were recorded on a Bruker Avance 300 spectrometer operating at 300 MHz for 1H. The 1H NMR spectra were
recorded using a sweep width of 12 000 Hz and a 90 pulse. The
samples were prepared by dissolving crystalline material in the
appropriate solvent (CDCl3 or/and CD3OD) just prior to the NMR
experiment.
2.16. EPR spectroscopy

Fig. 3. Ortep drawing (50% of probability) of 8. Hydrogen atoms have been omitted
for clarity.

2.14. X-ray crystallography


Intensity data for all compounds were measured employing an
XCalibur III 4-cycle diffractometer, equipped with a CCD camera
detector, using a monochromatized Mo Ka (k = 0.71073 ) radiation at 100 K. In all cases, analytical absorption corrections were
applied. The structures were solved by direct methods using the
program SHELX-97 and rened on F2 by a full-matrix least-squares
procedure with anisotropic displacement parameters for all the
non-hydrogen atoms based on all data minimizing wR = [Rw(|Fo|2
 |Fc|2)/Rw|Fo|2]1/2,
F 2c )2]/(n

R = R||Fo|  |Fc||/R|Fo|,
2

(F 2o )

and

GOF = [R[w(F 2o


 p)] , w = 1/[r
+ (aP) + bP], where P = (F 2o + 2F 2c )/
3 [13,14]. A summary of the relevant crystallographic data and
1/2

The cw X-band EPR spectra of compounds 1315 were measured on an ELEXSYS E500 Bruker spectrometer at resonance frequency 9.5 GHz and modulation frequency 100 MHz. Powder
samples were measured at room temperature and at 135 K. The
optimization of the spin Hamiltonian parameters and EPR data
simulation were performed by using the software package easyspin 4.0.0 [15]. For generation of the simulated powder EPR spectrum the following spin Hamiltonian was used:

H g 0 bBS DS2z  SS 1=3 ES2x  S2y

where g is the g-value of the S-state, D and E are the zero-eld splitting parameters.
2.17. Luminescence experiments
Luminescence spectra were recorded on a Jasco FP-6300 Spectrouorometer. The relative uorescence yield of Ln3+ complexes
was estimated towards the standard [Eu(acac)33H2O] (1.00 mM,
Uref = 0.05% in CH3CN) [16]. Relative uorescence yields of the
Ln3+ complexes were calculated using the following equation [17].

860

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865

Fig. 4. Ortep drawing (50% of probability) of 10. Hydrogen atoms have been omitted for clarity.

Fig. 5. Ortep drawing (50% of probability) of 11. Hydrogen atoms have been omitted for clarity.

Ux Astd =Ax F x =F std nx =nstd 2 Ustd

where U is the relevant uorescence yield, A is the absorbance at


the excitation wavelength (280 nm), F is the area of the most
intense peak of the emission spectrum (647 and 613 for Sm3+ and
Eu3+ complexes respectively) and n is the refractive index of the
std (standard) and x (unknown) solutions (n = 1.344 CH3CN,
n = 1.329 CH3OH).
Measurements of the CH3OH and CH3CN solutions (1.0  105
up to 1.0  103 M) of the complexes were conducted at room
temperature. Crystalline material of the compounds were dissolved just prior the measurement. Because of their slow decomposition, the luminescence of the methanol solutions of
complexes 3, 6, 9 and 12 was measured within the rst ve minutes after their dissolution.

3. Results and discussion


3.1. Synthesis
The two step synthesis of the complexes 112 is summarized
in Scheme 2. EuCl3, Sm(NO3)3 and Gd(NO3)3 were used as lanthanide starting material for the synthesis of the complexes. Reaction
of the lanthanide salts with the heterocyclic tridentate, 135-tptz,
124-tptz and the bidentate dptz azo-heterocyclic ligands results
in the synthesis of complexes formulated as [Ln(L)lX3nSm]Xn
(X = Cl, NO3; S = MeOH; l = 12, n = 01, m = 02; L stands for
the azo-heterocyclic ligands; Ln = Eu3+, Sm3+). In addition to the
heterocyclic ligands and the chlorine or nitrate ions, solvent molecules complete the coordination sphere of the lanthanide ions.
Reaction of these compounds with tfac in methanol results in

861

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865


Table 2
Selected bond lengths and angle parameters for 6.

Table 3
Selected bond lengths and angle parameters for 7.

Parameter

Value ()

Parameter

Value ()

Parameter

Value ()

Parameter

Value ()

Sm(1)N(1)
Sm(1)N(4)
Sm(1)N(5)
Sm(1)N(8)
Sm(1)O(1)
Sm(1)O(2)
Sm(1)O(4)
Sm(1)O(5)
Sm(1)O(7)
Sm(1)O(8)

2.586(2)
2.593(2)
2.570(2)
2.613(2)
2.499(2)
2.516(2)
2.496(2)
2.501(2)
2.514(2)
2.502(2)

Sm(2)N(12)
Sm(2)N(15)
Sm(2)N(16)
Sm(2)N(19)
Sm(2)O(10)
Sm(2)O(11)
Sm(2)O(13)
Sm(2)O(14)
Sm(2)O(16)
Sm(2)O(18)

2.573(2)
2.607(2)
2.565(2)
2.600(2)
2.484(2)
2.539(2)
2.479(2)
2.520(2)
2.565(2)
2.551(2)

EuN(2)
EuN(6)
EuN(1)
EuO(5)
EuO(6)

2.578(3)
2.593(4)
2.602(3)
2.480(3)
2.471(3)

EuO(1)
EuO(2)
EuO(3)
EuO(4)

2.427(3)
2.396(3)
2.390(3)
2.420(3)

Value ()
O(4)Sm(1)O(1)
O(4)Sm(1)O(5)
O(1)Sm(1)O(5)
O(4)Sm(1)O(8)
O(1)Sm(1)O(8)
O(5)Sm(1)O(8)
O(4)Sm(1)O(7)
O(1)Sm(1)O(7)
O(5)Sm(1)O(7)
O(8)Sm(1)O(7)
O(4)Sm(1)O(2)
O(1)Sm(1)O(2)
O(5)Sm(1)O(2)
O(8)Sm(1)O(2)
O(7)Sm(1)O(2)
O(4)Sm(1)N(5)
O(1)Sm(1)N(5)
O(5)Sm(1)N(5)
O(8)Sm(1)N(5)
O(7)Sm(1)N(5)
O(2)Sm(1)N(5)
O(4)Sm(1)N(1)
O(1)Sm(1)N(1)
O(5)Sm(1)N(1)
O(8)Sm(1)N(1)
O(7)Sm(1)N(1)
O(2)Sm(1)N(1)
N(5)Sm(1)N(1)
O(4)Sm(1)N(4)
O(1)Sm(1)N(4)
O(5)Sm(1)N(4)
O(8)Sm(1)N(4)
O(7)Sm(1)N(4)
O(2)Sm(1)N(4)
N(5)Sm(1)N(4)
N(1)Sm(1)N(4)
O(4)Sm(1)N(8)
O(1)Sm(1)N(8)
O(5)Sm(1)N(8)
O(8)Sm(1)N(8)
O(7)Sm(1)N(8)
O(2)Sm(1)N(8)
N(5)Sm(1)N(8)
N(1)Sm(1)N(8)
N(4)Sm(1)N(8)

73.03(6)
51.42(6)
112.00(7)
113.98(7)
172.55(6)
75.22(6)
77.97(7)
131.01(6)
76.23(7)
51.20(6)
74.24(7)
51.09(6)
76.17(7)
131.86(6)
149.19(6)
135.72(7)
103.56(6)
142.68(7)
69.80(7)
72.00(7)
138.49(7)
139.96(7)
70.04(7)
133.43(7)
103.82(7)
139.70(7)
70.83(7)
69.26(7)
121.48(6)
112.32(7)
76.10(6)
66.80(7)
116.43(7)
69.23(7)
101.02(7)
62.05(7)
77.61(6)
67.23(6)
122.81(7)
110.94(7)
68.55(7)
117.05(7)
61.55(7)
101.42(7)
160.53(6)

Value ()
O(13)Sm(2)O(10)
O(13)Sm(2)O(16)
O(10)Sm(2)O(16)
O(13)Sm(2)O(14)
O(10)Sm(2)O(14)
O(16)Sm(2)O(14)
O(13)Sm(2)O(11)
O(10)Sm(2)O(11)
O(16)Sm(2)O(11)
O(14)Sm(2)O(11)
O(13)Sm(2)O(18)
O(10)Sm(2)O(18)
O(16)Sm(2)O(18)
O(14)Sm(2)O(18)
O(11)Sm(2)O(18)
O(13)Sm(2)N(16)
O(10)Sm(2)N(16)
O(16)Sm(2)N(16)
O(14)Sm(2)N(16)
O(11)Sm(2)N(16)
O(18)Sm(2)N(16)
O(13)Sm(2)N(12)
O(10)Sm(2)N(12)
O(16)Sm(2)N(12)
O(14)Sm(2)N(12)
O(11)Sm(2)N(12)
O(18)Sm(2)N(12)
N(16)Sm(2)N(12)
O(13)Sm(2)N(19)
O(10)Sm(2)N(19)
O(16)Sm(2)N(19)
O(14)Sm(2)N(19)
O(11)Sm(2)N(19)
O(18)Sm(2)N(19)
N(16)Sm(2)N(19)
N(12)Sm(2)N(19)
O(13)Sm(2)N(15)
O(10)Sm(2)N(15)
O(16)Sm(2)N(15)
O(14)Sm(2)N(15)
O(11)Sm(2)N(15)
O(18)Sm(2)N(15)
N(16)Sm(2)N(15)
N(12)Sm(2)N(15)
N(19)Sm(2)N(15)

140.54(6)
72.15(6)
73.75(6)
51.08(6)
124.98(6)
107.45(6)
128.55(6)
51.02(6)
68.39(6)
174.51(6)
70.38(6)
72.86(6)
50.65(6)
68.69(6)
105.85(6)
75.71(6)
143.75(6)
135.69(7)
72.82(6)
112.64(6)
139.38(7)
141.66(7)
77.78(6)
139.38(7)
112.53(6)
71.24(6)
142.41(6)
65.98(7)
70.85(6)
120.61(6)
78.64(6)
113.09(6)
70.12(6)
123.10(7)
62.31(7)
91.95(6)
118.19(6)
72.50(6)
131.35(6)
67.20(6)
112.51(6)
86.19(6)
90.71(7)
62.62(6)
149.61(6)

Value ()
O(3)EuO(2)
O(3)EuO(4)
O(2)EuO(4)
O(3)EuO(1)
O(2)EuO(1)
O(4)EuO(1)
O(3)EuO(6)
O(2)EuO(6)
O(4)EuO(6)
O(1)EuO(6)
O(3)EuO(5)
O(2)EuO(5)
O(4)EuO(5)
O(1)EuO(5)
O(6)EuO(5)
O(3)EuN(2)
O(2)EuN(2)
O(4)EuN(2)

94.8(1)
70.5(1)
69.3(1)
68.4(1)
70.3(1)
118.1(1)
74.4(1)
140.6(1)
71.4(1)
133.8(1)
139.1(1)
74.8(1)
135.5(1)
70.8(1)
136.7(1)
133.2(1)
132.0(1)
121.3(1)

Value ()
O(1)EuN(2)
O(6)EuN(2)
O(5)EuN(2)
O(3)EuN(6)
O(2)EuN(6)
O(4)EuN(6)
O(1)EuN(6)
O(6)EuN(6)
O(5)EuN(6)
N(2)EuN(6)
O(3)EuN(1)
O(2)EuN(1)
O(4)EuN(1)
O(1)EuN(1)
O(6)EuN(1)
O(5)EuN(1)
N(2)EuN(1)
N(6)EuN(1)

120.6(1)
69.1(1)
67.7(1)
80.4(1)
141.7(1)
140.2(1)
72.6(1)
75.1(1)
84.2(1)
62.8(1)
142.0(1)
80.9(1)
72.8(1)
140.9(1)
85.1(1)
76.5(1)
62.3(1)
125.1(1)

Table 4
Selected bond lengths and angle parameters for 8.
Parameter

Value ()

Parameter

Value ()

EuN(2)
EuN(5)
EuN(1)
EuO(2)
EuO(6)

2.642(3)
2.608(3)
2.633(3)
2.384(2)
2.386(2)

EuO(3)
EuO(4)
EuO(5)
EuO(1)

2.386(2)
2.400(2)
2.408(2)
2.414(2)

Value ()
O(2)EuO(6)
O(2)EuO(3)
O(6)EuO(3)
O(2)EuO(4)
O(6)EuO(4)
O(3)EuO(4)
O(2)EuO(5)
O(6)EuO(5)
O(3)EuO(5)
O(4)EuO(5)
O(2)EuO(1)
O(6)EuO(1)
O(3)EuO(1)
O(4)EuO(1)
O(5)EuO(1)
O(2)EuN(5)
O(6)EuN(5)
O(3)EuN(5)

73.90(9)
107.68(9)
141.44(9)
140.35(9)
131.14(8)
72.63(9)
70.89(9)
72.13(8)
72.35(9)
139.43(9)
69.89(9)
138.68(9)
70.48(9)
73.40(9)
112.59(9)
75.75(9)
76.15(9)
142.31(9)

Value ()
O(4)EuN(5)
O(5)EuN(5)
O(1)EuN(5)
O(2)EuN(1)
O(6)EuN(1)
O(3)EuN(1)
O(4)EuN(1)
O(5)EuN(1)
O(1)EuN(1)
N(5)EuN(1)
O(2)EuN(2)
O(6)EuN(2)
O(3)EuN(2)
O(4)EuN(2)
O(5)EuN(2)
O(1)EuN(2)
N(5)EuN(2)
N(1)EuN(2)

81.53(9)
138.93(9)
76.22(9)
142.56(9)
80.43(9)
76.68(9)
77.00(9)
75.59(9)
140.85(9)
123.95(9)
124.97(9)
62.94(8)
127.33(9)
68.20(9)
120.98(9)
126.37(9)
62.54(9)
61.44(9)

3.2. X-Ray crystallography


the formation of the [Eu(135-tptz)(MeOH)2(tfac)2]Cl, [Sm(135tptz)(NO3)(tfac)2], and [Ln(L)l(tfac)3] complexes. Almost all compounds, except the Ln3+ complexes of dptz, are stable in solid
state and in solution. Complexes 3, 6, 9 and 12 decompose in
protic solvents slowly releasing free dptz in solution. The rate
of the decomposition was monitored by 1H NMR and UVVis
spectroscopy (Fig. S1, complex 12). In the rst 10 min the decomposition was less than 5% and after 2.5 h was ranged between 20%
and 30% of the initial concentration depending on the type of the
complex; diketonate decompose slower than the non-diketonate
complexes.

The ORTEP structures of complexes 68, 10, 11 are shown in


Figs. 15. Crystallographic data are provided in Table 1. Tables 2
6 contain selected bond lengths and angles of complexes 68, 10
and 11.
Two crystallographically-independent samarium complexes are
crystallized in the unit cell of 6. Both molecules own the same
structure with differences in the bond distances and the angles.
The coordination number of each samarium ion is 10. Four out of
the 10 positions are occupied by the pyridine and the triazine diazole type nitrogen of the two dptz ligands. Three chelate nitrate

862

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865

Table 5
Selected bond lengths and angle parameters for 10.
Parameter

Value ()

Parameter

Value ()

SmN(2)
SmN(6)
SmN(1)
SmO(3)
SmO(2)

2.621(4)
2.626(4)
2.632(4)
2.366(3)
2.397(3)

SmO(4)
SmO(1)
SmO(6)
SmO(5)

2.396(3)
2.421(3)
2.519(3)
2.545(3)

Value ()
O(3)SmO(2)
O(3)SmO(4)
O(2)SmO(4)
O(3)SmO(1)
O(2)SmO(1)
O(4)SmO(1)
O(4)SmO(6)
O(3)SmO(6)
O(2)SmO(6)
O(1)SmO(6)
O(3)SmO(5)
O(2)SmO(5)
O(4)SmO(5)
O(1)SmO(5)
O(6)SmO(5)
O(3)SmN(2)
O(2)SmN(2)
O(4)SmN(2)

84.9(1)
73.9(1)
70.6(1)
72.1(1)
69.9(1)
129.2(1)
78.4(1)
120.0(1)
132.5(1)
152.1(1)
70.2(1)
138.3(1)
70.6(1)
138.3(1)
50.6(1)
146.4(1)
115.0(1)
136.9(1)

Value ()
O(1)SmN(2)
O(6)SmN(2)
O(5)SmN(2)
O(3)SmN(6)
O(2)SmN(6)
O(4)SmN(6)
O(1)SmN(6)
O(6)SmN(6)
O(5)SmN(6)
N(2)SmN(6)
O(3)SmN(1)
O(2)SmN(1)
O(4)SmN(1)
O(1)SmN(1)
O(6)SmN(1)
O(5)SmN(1)
N(2)SmN(1)
N(6)SmN(1)

89.0(1)
67.3(1)
103.6(1)
85.2(1)
140.3(1)
141.5(1)
70.5(1)
85.0(1)
72.0(1)
62.0(1)
151.1(1)
70.1(1)
83.9(1)
110.7(1)
71.6(1)
119.7(1)
61.4(1)
123.3(1)

Table 6
Selected bond lengths and angle parameters for 11.
Parameter

Value ()

Parameter

Value ()

SmN(2)
SmN(5)
SmN(1)
SmO(3)
SmO(2)

2.656(3)
2.627(3)
2.649(3)
2.390(3)
2.394(3)

SmO(5)
SmO(4)
SmO(1)
SmO(6)

2.394(3)
2.409(3)
2.416(3)
2.422(3)

Value ()
O(3)SmO(2)
O(3)SmO(5)
O(2)SmO(5)
O(3)SmO(4)
O(2)SmO(4)
O(5)SmO(4)
O(3)SmO(1)
O(2)SmO(1)
O(5)SmO(1)
O(4)SmO(1)
O(3)SmO(6)
O(2)SmO(6)
O(5)SmO(6)
O(4)SmO(6)
O(1)SmO(6)
O(3)SmN(5)
O(2)SmN(5)
O(5)SmN(5)

141.55(9)
107.90(9)
73.95(9)
72.26(9)
131.24(9)
140.30(9)
72.78(9)
71.86(9)
70.95(9)
139.46(9)
70.58(10)
138.56(9)
69.74(9)
73.44(9)
112.83(9)
142.32(9)
76.09(9)
75.81(9)

Value ()
O(4)SmN(5)
O(1)SmN(5)
O(6)SmN(5)
O(3)SmN(1)
O(2)SmN(1)
O(5)SmN(1)
O(4)SmN(1)
O(1)SmN(1)
O(6)SmN(1)
N(5)SmN(1)
O(3)SmN(2)
O(2)SmN(2)
O(5)SmN(2)
O(4)SmN(2)
O(1)SmN(2)
O(6)SmN(2)
N(5)SmN(2)
N(1)SmN(2)

81.63(9)
138.77(9)
76.28(9)
76.87(10)
80.36(9)
142.93(9)
76.60(9)
75.94(9)
141.02(9)
123.34(9)
127.28(9)
62.81(9)
124.80(9)
68.43(9)
120.74(9)
126.35(9)
62.25(9)
61.11(9)

groups complete the coordination sphere of the metal ion. The


bond distances between Sm3+ and diazole nitrogen atom [Sm
N(1) 2.586(2) and SmN(5) 2.570(2) ] are signicantly shorter
than SmNpyridine lengths [SmN(4) 2.593(2) and SmN(8)
2.613(2) ]. Up to now, all crystal structures of the Ln3+ 1,2,4-triazine complexes, including 6, show Ln3+ to be ligated by the diazole nitrogen atoms [1821]. Apparently, lanthanide ions interact
stronger with the diazole than the pyridine nitrogen atom of the
triazine ligand.
The coordination number of the lanthanide ions in the rest of
the structures is nine. The coordination environment around Eu3+
in 7 and Sm3+ in 10 is consisted by three 135-tptz nitrogen donor
atoms and four tfac oxygen atoms while the last two positions are
occupied by oxygen atoms from methanol groups in 7 or by the

chelate nitrate group in 10. The SmN(2) bond length


[2.621(4) ] (triazine nitrogen atom) is shorter than the bond distances between the Sm3+ and the pyridine nitrogen atoms [Sm
N(6) 2.626(4) and SmN(1) 2.632(4) ]. Although the EuN bond
distances in 7 are shorter than the respective SmN in 10, a similar
trend is observed [EuN(2) 2.578(3) , EuN(6) 2.5693(4) and
EuN(1) 2.602(3) ]. A collection of LnNtriazine, LnNpyridine bond
lengths (Ln = Eu, Sm) of all crystallographically characterized
135-tptz complexes, shown in Table 7, provides sufcient evidence
for stronger bonding of the lanthanides with the triazine than the
pyridine nitrogen atom. Another interesting feature of the structure of these complexes is that all aromatic rings of the 135-tptz
are located within a plane. As a consequence, the planarity of
135-tptz permits strong p-stacking interactions between the free
pyridyl and the ligated triazine and pyridyl rings to take place
(Fig. 6).
The coordination environments of Eu3+ (8) and Sm3+ (11) involve three nitrogen donor atoms originated from the 124-tptz
and six oxygen atoms originated from the three tfac chelate ligands. The 124-tptz ligates the lanthanide in a tridentate fashion
through the two pyridyl nitrogen atoms and the pyridine nitrogen
atom of the triazine ring. This is the rst example reported in the
literature of a lanthanide complex ligated from the pyridine nitrogen atom of the 1,2,4-triazine ligand. In contrast to 135-tptz and
dptz complexes, the SmN(2) bond length (triazine nitrogen atom)
[2.656(3) ] is larger than the SmN(5) [2.627(3) ] and SmN(1)
[2.649(3) ] (pyridine nitrogen atoms). The EuN bond distances
are shorter than the respective SmN due to the lanthanide contraction. In a similar mode the EuN(2) [2.647(3) ] bond is larger
than the EuN(5) [2.608(3) ] and EuN(1) [2.633(3) ]. The Ln
Ntriazine bond distances are the largest ever observed for triazine
complexes supporting that the pyridine type nitrogen atom of
the 1,2,4-triazine is a weak donor atom (Table 7). The weak bonding is also attributed to the severe distortion of the triazine ring
from planarity as a consequence of the steric interactions between
the two neighboring N(1)C(16) and N(6)C(1418) pyridyl
groups. The N(3) (diazole atom) deviates 0.259(3) in 8 and
0.0254(3) in 11 from the plane dened by the C(6)N(2)C(7)
C(8) atoms. The distortion caused by the tridentate ligation of
124-tptz is shown in Fig. 7. This is revealed by direct comparison
of the structure of 124-tptz in 8 with that of dptz in 6, where dptz
structure is considered to be in the relaxed form.
Another interesting feature of the structures of these diketonate
complexes is the different number of diketonates ligate to the Ln3+.
Although all complexes were synthesized under the same conditions, 135-tptz complexes contain two while the 124-tptz three
tfac ligands. This difference is attributed to the lower rigidity of
the non-planar 124-tptz compare to the planar 135-tptz. In particular, the plane dened from the N(1)C(15) pyridyl ring forms an
angle 15.1(1) in 8 and 15.4(1) in 11, with the plane dened from
the N(5)C(913) pyridyl ring allocating more space for the coordination of the third tfac.
3.3. 1H NMR and EPR spectroscopy
The 1H NMR spectra of the solutions of the Eu3+ and Sm3+ complexes (1 mM) in CD3OD and/or CDCl3, gave broad peaks paramagnetic low eld shifted (Figs. S2S4). The absence of peaks of the
free triazine ligand in the aromatic region indicates that the complexes at these conditions, concentration and solvent, are stable.
The protons in ortho position to the pyridine donor nitrogen atoms
were very broad and in the most spectra were not observed. The
nuclei far from the metal ions coordination environment gave relatively sharp peaks slightly downeld shifted related to the peaks
of the free ligand. The tfac ligand also gave broad peaks. The
methylene proton of tfac of the tptz complexes show a very large

863

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865


Table 7
Comparative bond lengths of Eu3+ and Sm3+ complexes of 1,3,5-triazine derivatives.a
Compound

Value ()

Value ()

Refs.

7
[Eu(L1)(NO3)3(H2O)]
[Eu(L2)(NO3)2(H2O)3] [NO3]
[Eu(L1)(Cl)3(CH3OH)2]
[Eu(L1)(dphac)3]
[Eu(L1)(thienfac)3]
[Eu(L1)(phacH)3]
[Eu(L1)(phfac)3]CH3CH2OH
[Eu(L1)(dtfac)2(CH3CH2OH)(H2O)]
[Eu(L1)(dtfac)3]
{[Eu(L1)(H2O)4Fe(CN)6]6H2O}1

LnN1,3,5-triazine
2.578(3)
2.579(2)
2.531(8)
2.555(4)
2.676(2)
2.579(9)
2.618(11)
2.607(3)
2.535(3)
2.539(2)
2.577(5)

LnNpy
2.593(4),
2.618(2),
2.590(7),
2.646(4),
2.708(2),
2.633(7),
2.684(1),
2.630(4),
2.581(4),
2.582(3),
2.621(6),

2.602(3)
2.576(2)
2.580(7)
2.617(4)
2.697(2)
2.602(7)
2.661(1)
2.629(3)
2.570(4)
2.576(2)
2.607(6)

this work
[23]
[24]
[25]
[9]
[8]
[8]
[8]
[10]
[10]
[26]

10
[Sm(L1)(NO3)3(H2O)]
[Sm(L2)(NO3)3(H2O)]
[Sm(L2)(NO3)2(H2O)3][NO3]
{[Sm(L1)(H2O)4Fe(CN)6]8H2O}1
{[Sm(L1)(H2O)4Co(CN)6]8H2O}1

2.621 (4)
2.603(2)
2.523(4)
2.548(8)
2.587(5)
2.580(5)

2.626(4),
2.629(2),
2.601(3),
2.590(9),
2.637(6),
2.627(6),

2.632(4)
2.593(2)
2.581(4)
2.562(8)
2.627(6)
2.614(5)

this work
[23]
[24]
[24]
[26]
[26]

Ln-N1,2,4-triazine
2.586(2), 2.570(2)
2.573(2), 2.565(2)

2.593(2), 2.613(2)
2.607(2), 2.600(2)

this work

8
[Eu(L3)(NO3)3]
[Eu(L4)2(NO3)][Eu(NO3)5]

2.642(3)
2.602(11)
2.615(6), 2.615(8), 2.572(6), 2.545(8)

2.608(3), 2.633(3)
2.605(9)
2.598(6), 2.571(7), 2.561(7)

this work
[21]
[20]

11
[Sm(L3)(NO3)3]
[Sm(L5)3][Sm(NO3)5]

2.656(3)
2.617(4)
2.595(11), 2570(11), 2.568(10), 2.567(11), 2.564(10)

2.627(3), 2.649(3)
2.595(4)
2.588(10), 2.580(12), 2.553(11)

this work
[19]
[18]

a
Ligand abbreviations: L1 = 2,4,6-tris(2-pyridyl)-1,3,5-triazine, L2 = 4-Amino-2,6-bis(2-pyridyl)-1,3,5-triazine, dphac = 1,3-diphenyl-1,3-propanedione, thienfac = 1-thienoyl-4,4,4-triuoro-butanedione, phacH = 1-phenyl-1,3-butanedione, phfac = 1-phenyl-4,4,4-triuoro-1,3-butanedione, dtfac = 1,1,1,5,5,5-hexauoro-2,4-pentanedione.
L3 = (5,6-diethyl-1,2,4-triazine-3-yl)-2,20 -dipyridine, L4 = 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazine-3-yl)-1,10-phenanthroline, L5 = 2,6-bis(5,6dipropyl-1,2,4-triazine-3-yl)-pyridine.

downeld shift (32 ppm) attributed to the strong bonding of the


ligand with the lanthanides and the electron delocalization in the
tfac chelate ring.
The EPR powder spectra of complex 13 at room temperature
and 130 K are shown in Figs. 8 and 9 respectively. The EPR spectra
of the Gd3+ complexes consist of a main asymmetric, broad line
with unresolved structure centered at g  2 and many additional
unresolved lines at lower (g  3.0 and g  5.5) and higher
(g  1.5) magnetic elds. The EPR spectra with three and more
absorption signals are assigned to the isolated magnetically noninteracting Gd3+ ions. Spinspin interactions between GdGd ions
are expected to give broader less resolved absorptions signal at
g  2. The relative high zero eld splitting parameters
(D  1550 MHz, E  260 MHz) indicate a strong crystal eld and
asymmetric environment [22] which is consistent with the crystallographic data of the respective Eu3+ and Sm3+ complexes.
3.4. UVVis and luminescence spectroscopy

Fig. 6. Structure drawings of (A) 7 [C(3)- - -C(9) = 3.373(6) , C(1)- - C(13) = 3.370(6) ]
and
(B)
10
[C(4)- - -C(10) = 3.365(6) ,
C(6)- - C(9) = 3.376(6) ] illustrating the p-stacking interactions between two molecules.

The data of the maximum absorbance peak of the UVVis spectra of the complexes are summarized in Table 8. The UVVis spectra of the complexes and the ligands are shown in Fig. S5. The
spectra of the complexes are similar to those of the ligands indicating that all peaks may be assigned to intraligand transitions. The
spectra of 712 contain essentially the combined ligand absorptions, slightly red shifted due to metal complexation.
Fluorescence intensity and relative luminescence yields of the
complexes are summarized in Table 8. The uorescence spectrum
of complex 9 is shown in Fig. 10. Excitation of Eu3+ complexes is
followed by strong red luminescence which exhibits the characteristic luminescence spectrum of the Eu3+ ion corresponding to the
5
D0 ? 7FJ (J = 04) transitions with band maxima at 580 nm
5
( D0 ? 7F0), 593 nm (5D0 ? 7F1), 614 nm (5D0 ? 7F2), 653 nm

864

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865

Fig. 7. Drawing illustrating the overlap of the structures of 124-tptz (red) in 7 and of dptz (black) in 6 showing the severe distortion of 124-tptz due to the tridentate ligation.
(Color online.)

Fig. 8. Powder EPR spectrum at RT of 13 (black dots) and simulated spectra (red
line). The spectrum was simulated using the following parameters: g = 2.005,
D = 1558 MHz E = 262.8 MHz. (Color online.)

(5D0 ? 7F3) and 702 nm (5D0 ? 7F4). Excitation of Sm3+ complexes


leads to a strong pink emission of Sm3+ corresponding to 4G5/
6
2 ? HJ (J = 5/2, 7/2, 9/2, 11/2) transitions at 563, 605, 647 and
707 nm respectively. The most intense peak is at 647 nm and is assigned to the transition 4G5/2 ? 6H9/2.
The relative uorescence yield is dependent on the type and the
ligation of the triazine ligand. The tridentate 1,2,4-triazine complexes, 2, 5, 8, 11, exhibit stronger luminescence than the respective compounds of 1,3,5-triazine, 1, 4, 7, 10. This is unexpected
considering that 124-tptz is a weaker binder for the lanthanides
and less rigid than 135-tptz. Surprising, the bidentate dptz enhances the luminescence of the lanthanide ions 35 times more
than the respective tptz complexes. This is probably due to the
strong ligation of the diazole group to the metal-ion which seems
to satisfy the electronic requirements for facile energy transfer
from the ligand to the lanthanide ions.
Complexes containing both the triazine and that tfac ligands
exhibit more intense luminescence that may be attributed to a synergism of the two ligands or to the decrease of the vibrational
quenching processes. It is interesting to notice here that the relative uorescence yield is doubled with the co-coordination of tfac
and this enhancement is independent to the number of the ligated
diketonates. Thus, the ligation of the solvent molecules in the complexes with less than three tfac (7 and 10) does not show to
quench the luminescence through vibrational coupling. The Gd3+
complexes gave very weak luminescence that was attributed to
light emitted from the ligands.

Fig. 9. Powder EPR spectrum at 130 K of 13 (black dots) and simulated spectra (red
line). The spectrum was simulated using the following parameters: g = 2.005,
D = 1558 MHz, E = 262.8 MHz. (Color online.)

Table 8
Selected UVVis and luminescence data obtained from the spectra of the CH3CN
solutions of complexes 112. UV maximum absorption bands k (nm), molar
absorption coefcient e (M1 cm1), area of the most intense peak F, relative
uorescence yield of the most intense peak U% (most intense peaks = Sm3+ at 647 nm,
Eu3+ at 615 nm).
Complex

kmax (nm)

e  104 (M1 cm1)

Fa

U (%)a

1
2
3
4
5
6
7
8
9
10
11
12

290
286
284
284
286
284
288
291
290
290
292
291

11.3
21.3
17.4
8.6
10.5
10.8
14.6
14.5
11.7
11.8
10.9
11.2

2965
5899
13 193
828
2361
2678
5959
7186
25 923
3440
4408
7902

0.14
0.19
0.77
0.07
0.15
0.17
0.28
0.34
1.5
0.20
0.28
0.49

a
F and U have been calculated for the complexes excited at 280 nm in order to be
comparable with the luminescence of [Eu(acac)3] (yield 0.05%). Measurements of
the spectra excited at 380 nm gave yields 10 times larger than the values at
280 nm.

4. Summary
New Eu3+ and Sm3+ complexes formulated as [Ln(L)lXnSm]
(X = Cl, NO3, tfac; S = solvent; l = 12, n = 23, m = 02) have

L. Panayiotidou et al. / Polyhedron 52 (2013) 856865

865

Appendix A. Supplementary data


CCDC 888687888691 contains the supplementary crystallographic data for 6, 7, 8, 10 and 11. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.poly.2012.07.029.
References

Fig. 10. Excitation (monitoring the peak at 615 nm, black) and emission (after
excitation at 380 nm, red) luminescence spectrum of 0.10 mM solution of 9 in
CH3CN. (Color online.)

been synthesized. Complexes 68, 10 and 11 have been


characterized by single crystal X-ray crystallography. 1H NMR
and powder cw-EPR spectroscopies have been employed for the
characterization of the complexes in solution and solid state. The
structure of the triazine ligands found to be a key factor which controls the architecture of the complex. Both Eu3+ and Sm3+ complexes exhibit bright luminescence. The intensity and the relative
luminescence yield are dependent on the structure and the ligating
mode of the triazine ligand. The 1,2,4-triazines enhance the Eu3+
and Sm3+ luminescence more than the 1,3,5 triazines. More intensive luminescence has been recorded for the complexes containing
both the triazine and tfac ligands and can be attributed to a synergism of the two ligands and/or to the decrease of the vibrational
quenching processes. An investigation of the mechanism of the
lanthanide sensitization from the 1,2,4-triazine ligands is
underway.

Acknowledgements
This work has been supported by Research Promotion Foundation and European Regional Development Fund and the Republic of
Cyprus, Research Programs TEXNO/0506/19 and ANABAHMIRH/
PACIO/0308/32 (EPR).

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