Beruflich Dokumente
Kultur Dokumente
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
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
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.)
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.
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%.
858
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
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%.
859
Fig. 2. Ortep drawing (50% of probability) of 7. Hydrogen atoms have been omitted for clarity.
Fig. 3. Ortep drawing (50% of probability) of 8. Hydrogen atoms have been omitted
for clarity.
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:
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
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.
861
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)
862
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)
863
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.
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
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.)
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)
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
865
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.)
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).