Synthesis and characterization of two one-dimensional lanthanide coordination polymers

Article abstract of DOI:10.1016/j.jallcom.2004.03.093

Two lanthanide coordination polymers [Eu(H₂sal)(Hsal)(sal) ·H₂O]_n (1) and {[Tb(FUR)₃(H ₂O)₂]·DMF}_n (2) (H₂sal, salicylic acid; Hsal^-, o-HOC₆H

Full text of DOI:10.1016/j.jallcom.2004.03.093

Journal of Alloys and Compounds 381 (2004) 50–57
Synthesis and characterization of two one-dimensional lanthanide
coordination polymers
Mingcai Yin, Jutang Sun∗
Department of Chemistry, Wuhan University, Wuhan 430072, PR China
Received 26 January 2004; received in revised form 12 March 2004; accepted 12 March 2004
Abstract
Two lanthanide coordination polymers [Eu(H2sal)(Hsal)(sal)·H2O]n (1) and {[Tb(FUR)3(H2O)2]·DMF}n (2) (H2sal, salicylic acid; Hsal−,
o-HOC6H4CO2−; HFUR, ␣-furancarboxylic acid; DMF, N,N-dimethylformamide) were synthesized and characterized by elemental analysis,
TG, IR, andluminescence spectra. The crystal structures were determined byX-ray single crystal analysis. Bothcomplexes are one-dimensional
polymers. Probably the luminescence quenching of complex 1 is assigned to its special one-dimensional ribbon structure. The vibration energy
level caused by the one-dimensional ribbon and located between 5D0 and 7Fj maybe is the main reason. Complex 2 displays intense green
luminescence under the excitation of UV light. The emission bands at 486, 541, 584, and 618 nm are attributed to the characteristic 5D4 → Fj
7
(j = 6, 5, 4, 3) transitions of Tb(III) ions, respectively.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Coordination polymer; Lanthanide complexes; Crystal structure; Luminescence
1. Introduction
2. Experimental
Nowadays great attention has been paid to the lan-
thanide aromatic carboxylates owing to its novel struc-
tures and potential applications in material sciences such
as supraconductor, magnetic materials, and luminescent
probes [1–5]. Up to now, many lanthanide aromatic
carboxylates have been reported, which are commonly
in dimeric or polymeric forms [6–12]. As a part of
our studies on the structure and luminescence of lan-
thanide aromatic carboxylates, two one-dimensional co-
ordination polymers [Eu(H2sal)(Hsal)(sal)·H2O]n (1)
and {[Tb(FUR)3(H2O)2]·DMF}n (2) (H2sal, salicylic
acid; Hsal−, o-HOC6H4CO2−; HFUR, ␣-furancarboxylic
acid; DMF, N,N-dimethylformamide) were obtained.
The structures and luminescence properties are reported
here.
2.1. Materials and methods
EuCl3·5H2O and Tb2(CO3)3 were prepared in our lab-
oratory. All other chemicals were analytical reagent grade.
The IR spectra were recorded on a Thermo Nicolet Avatar
360 FT-IR spectrophotometer using KBr pellets. Elemen-
tal analyses were carried out with a Perkin-Elmer 240B
elemental analyzer. The thermogravimetric analyses were
conducted on a Shimadzu DT-40 thermal analyzer at a
heating rate of 20 ◦C/min in air. The X-ray powder diffrac-
tions were performed on a Shimadzu XRD-6000 powder
diffractionmeter. The excitation and emission spectra of the
solid sample were measured on a Shimadzu RF-5301PC
spectrofluorophotometer at room temperature.
2.2. Synthesis of [Eu(H2sal)(Hsal)(sal)·H2O]n (1)
An aqueous solution of EuCl3·5H2O (0.35 g, 1.0 mmol)
was added dropwise to an aqueous solution of Na[o-HOC6-
H4CO2] (0.50 g, 3.0 mmol) under stirring and light-yellow
precipitants were formed immediately. The mixture was
stirred for about 10 min at room temperature and filtered.
∗
Corresponding author. Tel.: +86-27-87218494;
fax: +86-27-87647617.
E-mail address: jtsun@whu.edu.cn (J. Sun).
0925-8388/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2004.03.093

M. Yin, J. Sun / Journal of Alloys and Compounds 381 (2004) 50–57
51
Table 1
Crystal data and structure refinement for 1
Compound
1
2
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system, space group
a (Å)
C
21H17EuO10
C18H20NO12Tb
601.27
293(2)
0.71073
Triclinic, p1
9.786(2)
581.31
291(2)
0.71073
Monoclinic, p21/n
13.633(3)
b (Å)
6.7476(13)
22.730(5)
90
100.06(3)
90
2058.8(7)
4, 1.875
3.104
11.122(2)
11.259(2)
76.81(3)
69.81(3)
75.72(3)
1100.8(4)
2, 1.814
3.276
c (Å)
α (◦)
β (◦)
γ (◦)
V (Å3)
Z, Dcalculated (g/cm3)
µ (mm−1
F(0 0 0)
)
1144
592
Crystal size (mm)
0.20 × 0.20 × 0.18
0.20 × 0.18 × 0.18
θ range for data collection (◦)
Index ranges
1.63–27.54
1.91–27.51
0 ≤ h ≤ 17, −8 ≤ k ≤ 8, −29 ≤ l ≤ 29
7712/4429
93.3
0.6050 and 0.5756
Full matrix least squares on F2
4429/0/290
−12 ≤ h ≤ 11, −14 ≤ k ≤ 0, −14 ≤ l ≤ 13
Reflections collected/unique
Completeness to max θ (%)
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
4386/4386
88.49
0.6146 and 0.6146
Full matrix least squares on F2
4386/0/290
1.158
1.212
Final R indices [I > 2σ(I)] (R1, wR2)
R indices (all data) (R1, wR2)
Extinction coefficient
Largest diff. peak and hole (e/Å3)
0.0402, 0.1117
0.0493, 0.1152
0.0046(4)
1.588 and −1.477
0.0369, 0.1039
0.0411, 0.1068
0.0373(17)
1.128 and −1.519
Light-yellow needle-like crystals were obtained from the
filtrate after about 2 weeks (0.15 g in the yield of 25.86%).
Elemental analysis for C21H17EuO10 (%): found (calc.): C
43.18 (43.38), H 3.01 (2.93). IR (KBr, cm−1): 3439.0 (m),
1623.9 (s), 1594.8.1 (s), 1565.3 (vs), 1548.7 (vs), 1512.0
(m), 1482.8 (s), 1465.0 (vs), 1426.4 (vs), 1387.6 (vs),
1307.1 (m), 1248.1 (m), 1216.3 (m), 1147.3 (m), 1032.7
(m), 883.3 (m), 852.5 (m), 806.2 (m), 756.0 (s), 704.0 (m),
663.5 (m), 572.8 (w), 528.5 (w), 484.1 (w), and 472.5 (m).
2.4. Crystallographic measurement and structure
resolution
The X-ray crystallography data for complexes 1 and 2
were collected on a RIGAKU R-AXIS IV imaging plate
diffractionmeter with graphite-monochromated Mo K␣ radi-
ation (λ = 0.71073 Å). The structures were solved by direct
methods and refined by full matrix least squares on F2 using
the SHELXL-97 and SHELXS-97 programs [13], respec-
tively. All non-hydrogen atoms were refined with anisotropic
displacement parameters. The hydrogen atoms were gener-
ated geometrically and treated by a mixture of independent
and constrained refinements. A summary of crystallographic
data and refinement details is given in Table 1. Selected bond
lengths and angles for 1 and 2 are listed in Tables 2 and 3,
respectively.
2.3. Synthesis of {[Tb(FUR)3(H2O)2]·DMF}n (2)
SrCl2·6H2O (0.26 g, 1.0 mmol), 0.24 g (0.5 mmol)
Tb2(CO3)3, 0.58 g (5.0 mmol) ␣-furancarboxylic acid, and
2.9 ml distilled water were mixed in a Teflon-lined stainless
steel container to get a rheological phase. The container
was sealed and reacted at 90 ◦C for 3 days. The white pow-
ders obtained were dissolved in a H2O/DMF (9:1) solvent
and evaporated at room temperature. Colorless prismatic
crystals were formed after several days [0.25 g in the yield
of 41.7% based on Tb2(CO3)3]. Elemental analysis for
C18H20NO12Tb (%): found (calc.) C 35.78 (35.92), H 3.21
(3.33), N 2.35 (2.33). IR (KBr, cm−1): 3134.1 (s), 1589.2
(vs), 1558.4 (vs), 1541.0 (vs), 1481.2 (vs), 1419.5 (vs),
1398.3 (vs), 1373.2 (vs), 1228.6 (m), 1199.6 (w), 1141.8
(w), 1078.1 (m), 1014.5 (m), 785.0 (s), 758.0 (m), 613.3
(w), 555.5 (w), and 470.6 (m).
3. Results and discussion
3.1. IR spectra
The IR spectra of salicylic acid, ␣-furancarboxylic
acid, and both complexes were determined over the range
4000–400 cm−1 using KBr pellets and the spectra of com-
plexes 1 and 2 in the range of 2000–400 cm−1 are shown in
Fig. 1. The absorption bands of M–O bond appear at 484.1

52
M. Yin, J. Sun / Journal of Alloys and Compounds 381 (2004) 50–57
Table 2
Selected bond lengths (Å) and bond angles (◦) for complex 1
Bond
Length
Bond
Length
Eu(1)–O(6)
2.353(4) Eu(1)–O(8)#1
2.410(4) Eu(1)–O(7)
2.427(4) Eu(1)–O(8)
2.431(3) Eu(1)–Eu(1)#1
2.470(4) Eu(1)–Eu(1)#2
2.478(4)
2.500(3)
Eu(1)–O(10)
Eu(1)–O(5)#1
Eu(1)–O(9)#2
Eu(1)–O(7)#2
Eu(1)–O(3)
2.546(3)
2.585(3)
4.2135(7)
4.2135(7)
Bond
Angle
Bond
Angle
O(2)–C(7)–O(3)
121.3(5)
123.2(5)
117.5(4)
67.23(13) O(5)#1–Eu(1)–O(3)
79.55(13) O(9)#2–Eu(1)–O(3)
83.98(14) O(7)#2–Eu(1)–O(3)
Eu(1)#1–O(7)–Eu(1) 114.26(12)
O(5)–C(14)–O(6)
O(7)–C(21)–O(8)
O(10)–Eu(1)–O(5)#1
O(6)–Eu(1)–O(9)#2
O(10)–Eu(1)–O(9)#2
O(6)–Eu(1)–O(3)
O(10)–Eu(1)–O(3)
123.06(14)
75.85(14)
71.13(13)
69.51(12)
126.92(11)
71.12(12)
O(5)#1–Eu(1)–O(9)#2 135.66(12) O(6)–Eu(1)–O(8)#1
O(6)–Eu(1)–O(7)#2
O(10)–Eu(1)–O(7)#2
75.04(13) O(10)–Eu(1)–O(8)#1 141.20(12)
72.35(13) O(5)#1–Eu(1)–O(8)#1 81.18(12)
O(5)#1–Eu(1)–O(7)#2 128.83(12) O(8)#1–Eu(1)–O(7)
O(9)#2–Eu(1)–O(8)#1 105.60(12) O(6)–Eu(1)–O(8)
O(7)#2–Eu(1)–O(8)#1 146.12(12) O(10)–Eu(1)–O(8)
64.30(11)
85.42(13)
83.72(13)
81.23(12)
129.96(12)
64.14(10)
150.30(13)
114.02(7)
50.02(11)
Fig. 1. The IR spectra of complexes 1 and 2.
O(3)–Eu(1)–O(8)#1
O(6)–Eu(1)–O(7)
O(10)–Eu(1)–O(7)
O(5)#1–Eu(1)–O(7)
O(9)#2–Eu(1)–O(7)
O(7)#2–Eu(1)–O(7)
O(3)–Eu(1)–O(7)
72.92(12) O(5)#1–Eu(1)–O(8)
74.52(13) O(9)#2–Eu(1)–O(8)
119.37(13) O(7)#2–Eu(1)–O(8)
68.74(12) O(3)–Eu(1)–O(8)
154.01(13) O(8)#1–Eu(1)–O(8)
108.18(9) O(7)–Eu(1)–O(8)
and 472.5 cm−1 for 1 and 470.6 cm−1 for 2. The absence
of band in the region 1690–1730 cm−1 for 2 indicates the
complete deprotonation of the COOH groups. The asym-
124.36(12) Eu(1)#1–O(7)–Eu(1) 114.26(12)
−
metric and symmetric stretching vibration bands of CO2
O(9)#2–Eu(1)–O(7)#2 65.89(11) Eu(1)#2–O(8)–Eu(1) 111.92(12)
Eu(1)#2–O(8)–Eu(1) 111.92(12)
groups appear at 1565.3, 1548.7, 1426.4, and 1387.6 cm−1
for 1 and 1558.4, 1541.0, 1419.5, 1398.3, and 137−3.2 cm−1
for 2, respectively, which indicates that the CO2 groups
function in different coordination modes. The strong ab-
sorption band which occurred at 1482.8 cm−1 indicates
the existence of uncoordinated phenolic hydroxyl group in
complex 1, consisting with the results of X-ray analyses in
the next section.
Table 3
Selected bond lengths (Å) and bond angles (◦) for complex 2
Bond
Length
Bond
Length
3.2. Structure description
Tb(1)–O(7)#1
Tb(1)–O(2)#2
Tb(1)–O(8)
2.282(4) Tb(1)–O(10)
2.295(5) Tb(1)–O(4)
2.327(4) Tb(1)–O(5)
2.346(4) O(2)–Tb(1)#2
2.453(4) O(7)–Tb(1)#1
2.469(5)
2.491(5)
2.495(5)
2.295(5)
2.282(4)
3.2.1. Structure of [Eu(H2sal)(Hsal)(sal)·H2O]n (1)
The structure of complex 1 is shown in Fig. 2. It is in
a low symmetry and there is no discrete europium sal-
icylate molecule in the crystal. It can be seen that the
salicylate ligands are in three coordination modes, namely
(a) monodentate salicylic acid molecule through its car-
bonyl oxygen atom, (b) bidentate bridging salicylate group
through two carboxyl oxygen atoms, and (c) pentadentate
chelating-bridging salicylate group through both the car-
boxyl and the phenolic oxygen atoms (as shown in Fig. 3),
the same as those in the lanthanide salicylates of Sm, Am,
La, and Nd [14].
It is different from the lanthanide salicylates of Tb and
Ho [15] but similar to those of Sm and Am [14] that
each Eu atom in complex 1 is surrounded by nine oxy-
gen atoms, one from a coordinated water molecule and
eight from six salicylate groups, in which one oxygen atom
(O3) is in the coordination mode (a), two oxygen atoms
Tb(1)−O(1)
Tb(1)–O(11)
Bond
Angle
Bond
Angle
O(2)–C(1)–O(1)
O(4)–C(6)–O(5)
124.9(5)
121.5(6)
124.7(5)
O(1)–Tb(1)–O(10)
O(11)–Tb(1)–O(10)
O(7)#1–Tb(1)–O(4)
81.39(16)
71.21(16)
78.61(16)
74.04(16)
128.61(17)
77.56(16)
130.15(14)
144.63(16)
73.28(17)
78.53(17)
78.24(17)
127.46(16)
145.09(16)
129.54(15)
52.50(14)
O(8)–C(11)–O(7)
O(7)#1–Tb(1)–O(8)
O(2)#2–Tb(1)–O(8)
O(7)#1–Tb(1)–O(1)
O(2)#2–Tb(1)–O(1)
O(8)–Tb(1)–O(1)
102.68(16) O(2)#2–Tb(1)–O(4)
83.68(17) O(8)–Tb(1)–O(4)
82.83(16) O(1)–Tb(1)–O(4)
104.94(16) O(11)–Tb(1)–O(4)
153.75(19) O(10)–Tb(1)–O(4)
O(7)#1–Tb(1)–O(11) 139.46(18) O(7)#1–Tb(1)–O(5)
O(2)#2–Tb(1)–O(11)
O(8)–Tb(1)–O(11)
O(1)–Tb(1)–O(11)
O(7)#1–Tb(1)–O(10)
O(2)#2–Tb(1)–O(10) 139.53(17) O(10)–Tb(1)–O(5)
O(8)–Tb(1)–O(10) 76.47(17) O(4)–Tb(1)–O(5)
71.21(17) O(2)#2–Tb(1)–O(5)
81.47(16) O(8)–Tb(1)–O(5)
78.15(16) O(1)–Tb(1)–O(5)
70.77(17) O(11)–Tb(1)–O(5)

M. Yin, J. Sun / Journal of Alloys and Compounds 381 (2004) 50–57
53
Fig. 2. Molecular structure of complex 1 with 15% thermal ellipsoids.
(O5B, O6) are in the mode (b), and the other five oxy-
gen atoms (O7, O8, O7B, O8A, O9B) are in the mode
(c). The Eu–O bonds vary from 2.353 to 2.585 Å and
the O–Eu–O angles range from 50.02 to 154.01◦ (see
Table 2 and Fig. 2). The Eu–O bonds of the chelating
carboxyl groups (2.546, 2.585 Å) are much longer than
that of the bridging carboxyl groups (2.353, 2.427 Å) and
the chelating-bridging ones (2.470, 2.500 Å), while the
Eu–O bond length of the aqua ligand (2.410 Å) is ap-
proximate to that of the phenolic group (2.431 Å). Every
two Eu atoms are linked together through three salicy-
late groups, one in mode (b) and two in mode (c) with
a Eu · · · Eu separation of 4.2135 Å, which results in the
formation of one-dimensional ribbon structure [Fig. 4(c)]
through the –Eu–O–C–O–Eu–O–C–O–Eu– [Fig. 4(a)] and
the –Eu–O–Eu–O–Eu– [Fig. 4(b)] chains.
In addition to the intramolecular hydrogen bonds formed
between the phenolic hydroxyl group and the carboxyl
group (O1 · · · O3 = 2.550 Å, O2 · · · O9B = 2.424 Å, and
O4 · · · O6 = 2.627 Å), aromatic stacking interactions ex-
ist between the phenyl rings containing C8–C13 with the
face-to-face distance being ca. 3.62 Å, which link the adja-
cent one-dimensional ribbons into two-dimensional layers,
as displayed in Fig. 5.
3.2.2. Structure of {[Tb(FUR)3(H2O)2]·DMF}n (2)
The molecular structure of complex 2 is shown in Fig. 6.
Each Tb atom in 2 is eight-coordinated by four oxygen atoms
Fig. 3. The coordination modes of salicylate ligand in complex 1.

54
M. Yin, J. Sun / Journal of Alloys and Compounds 381 (2004) 50–57
Fig. 4. Stereoscopic view of the (a) –Eu–C–O–O–Eu–O–C–O–Eu– chain, (b) –Eu–O–Eu–O–Eu– chain, and (c) one-dimensional ribbon along c-axis in
complex 1.
from four bridging FUR− groups, two oxygen atoms from
one chelating FUR− group, and two oxygen atoms from
two coordinated water molecules, the same as the lanthanide
atoms in complexes {[Eu(FUR)3·2H2O]·NO3(4,4ꢀ-bpy)}n
[7] and Ln(o-HOC6H4CO2)3(H2O)2·2H2O (Ln = Tb, Ho)
[15]. The Tb–O bonds range from 2.282 to 2.495 Å and
the O–C–O angles vary from 121.5 to 124.9◦. It is similar
to complex 1 that the average Tb–O bond of the chelating
FUR− groups (2.493 Å) is a bit longer than that of the bridg-
ing ones (2.313 Å) or the water ligands (2.461 Å).
Every two adjacent Tb atoms are linked together by
two bridging FUR− groups, which lead to the formation
of a one-dimensional chain, as illustrated in Fig. 7. For
the two Tb atoms bridged by the FUR− groups contain-
ing O1 and O2, the Tb1 · · · Tb1A separation is 4.882 Å,
but for the two Tb atoms bridged by the FUR− groups
containing O7 and O8, the Tb1. . . Tb1B separation is
4.972 Å. The DMF molecules located at both sides of
the one-dimensional chain do not coordinated to the Tb
atoms, but hydrogen bonds are formed not only between
its carbonyl oxygen atom and the two coordinated water
molecules (O12 · · · O10A = 2.75 Å, O12 · · · O11 = 2.76 Å;
Fig. 7), but also between its methyl groups and the furyl
oxygen atoms (C17–H · · · O6 = 2.840 Å). These hydro-
gen bonds link the adjacent one-dimensional chains into
two-dimensional layers, as displayed in Figs. 7 and 8.
Besides these hydrogen bonds, aromatic stacking interac-
tions exist between the furyl rings of two adjacent chains
with the average atom distance being 3.808 Å, which further
consolidate the two-dimensional architecture.
3.3. Thermogravimetric analysis (TGA)
The thermal behaviors of complexes 1 and 2 were stud-
ied from 30 to 800 ◦C in air, which agreed with the re-
sults of X-ray crystallography. The TG curves showed that
the weight loss of complex 1 begins at 166 ◦C and ends at
655 ◦C. It decomposes in four steps and the last residue is

M. Yin, J. Sun / Journal of Alloys and Compounds 381 (2004) 50–57
55
Fig. 5. Packing diagram of complex 1 along b-axis.
Fig. 8. Stereoscopic view of the hydrogen bonds and the aromatic stacking
interactions (some furyl rings are omitted for clarity).
Eu2O3 (observed, 30.0%; calculated, 30.26%: in accordance
with the JCPDS file 43-1008) [16]. Complex 2 begins to
lose weight at 79 ◦C and the weight loss from 79 to 164.8 ◦C
corresponds to the loss of two coordinated water molecules
and one solvent DMF molecule (observed, 16.14%; calcu-
lated, 16.09%). The decomposition of the framework begins
at 277.1 ◦C and ends at 643.7 ◦C. The last residue is Tb4O7
(observed, 31.06%; calculated, 31.10%: in agreement with
the JCPDS file 32-1286).
3.4. Photoluminescence
3.4.1. Luminescence quenching of complex 1
It is well known that europium salicylate has no lu-
minescence (both salicylate group and Eu3+ ion) when
irradiated by UV light, which has been attributed to the
energy mismatch between the lowest triplet state of sali-
cylate group and the lowest excited state (5D0) of Eu3+
ion [17]. However, we think that this explanation is ques-
tionable to some extent since if it is right, where is the
energy absorbed by the salicylate ligands and how to ex-
plain the red luminescence of the ionic dimeric europium
salicylate [Eu2(Hsal)8][Zn(phen)3]·(H2sal)(H2O) (phen:
1,10-phenanthroline), in which the phen ligand does not
coordinate to Eu3+ ions [18]. On the other hand, as far
as the energy transfer process, the energy absorbed by the
salicylate groups can be transferred to other higher excited
state energy levels of Eu3+ ion.
Fig. 6. The coordination environment around Tb atom in complex 2 with
10% probability thermal ellipsoids.
Since compound property has close relations to its struc-
ture, we attempted to interpret this luminescence quench-
ing from the influence of crystal structure and compared
the structure of complex 1 with those of other europium
aromatic carboxylates and terbium salicylate [15]. It is
found that some differences exist. First, in complex 1,
Fig. 7. Stereoscopic view of the one-dimensional chain along a-axis in
complex 2.

56
M. Yin, J. Sun / Journal of Alloys and Compounds 381 (2004) 50–57
Fig. 9. The possible energy level diagram and energy transfer mechanism for complex 1.
the salicylate group in the coordination mode (c) (Fig. 3)
exhibits a better coplanarity than the ligands in the other
lanthanide aromatic carboxylates owing to the coordina-
tion of phenolic oxygen atoms. In addition, besides the
–Eu–O–C–O–Eu–O–C–O–Eu– chains usually occurring in
lanthanide aromatic carboxylates, the –Eu–O–Eu–O–Eu–
chains are also present (Fig. 4), which result in the for-
mation of one-dimensional ribbon structure in complex 1.
Compared with the one-dimensional chain in the other lan-
thanide aromatic carboxylates such as Eu(TPA)3(HTPA)2
(HTPA, ␣-thiophene carboxylic acid), which emits an in-
tense red luminescence when irradiated by UV light [19],
the one-dimensional ribbon maybe has a much higher vi-
bration energy level (denoted as V) and probably it is just
3.4.2. Luminescence of complex 2
Under the excitation of UV light, complex 2 emits an in-
tense green luminescence. The excitation and emission spec-
tra of the solid sample are shown in Fig. 10. The excitation
bands at about 264, 303 nm are assigned to the n → ␲∗,
∗
␲ → ␲ transitions of furoate groups and the sharp peaks
located at 317, 338, 351, 368, and 485 nm are attributed to
7
7
7
7
the F6
→
5H7, F6
→
5L6, F6
→
5L9, F6
→
5L10,
7
5
and F6 → D4 transitions of Tb3+ ions, respectively. The
emission bands at 486, 541, 584, and 618 nm correspond to
5
7
the characteristic D4 → Fj (j = 6, 5, 4, 3) transitions of
Tb3+ ions, respectively.
5
7
located between D0 and Fj, which leads to the lumines-
cence quenching or a large red-shift of the luminescence
of Eu3+ ions so that it exceeds the effective measurement
range (220–750 nm; as shown in Fig. 9) [20,21].
4. Conclusion
Two one-dimensional lanthanide complexes [Eu(H2sal)-
(Hsal)(sal)·H2O]n (1) and {[Tb(FUR)3(H2O)2]·DMF}n (2)
have been synthesized and characterized by X-ray crystal-
lography. The one-dimensional ribbon architecture maybe is
the main reason for the luminescence quenching of complex
1. Complex 2 emits an intense green luminescence when
excited by UV light.
References
[1] J.P. Costes, J.M. Clemente-Juan, F. Dahan, F. Nicodme, M. Verelst,
Angew. Chem. Int. Ed. 41 (2002) 323.
[2] T.M. Reineke, M. Eddaoudi, M. Fehr, D. Kelly, O.M. Yaghi, J. Am.
Chem. Soc. 121 (1999) 1651.
[3] L. Ma, O.R. Evans, B.M. Foxman, W. Lin, Inorg. Chem. 38 (1999)
5837.
[4] J.S. Seo, D. Whang, H. Lee, S.I. Jun, J. Oh, Y.J. Jeon, K. Kim,
Nature 404 (2000) 982.
Fig. 10. The solid-state excitation and emission spectra of complex 2 (1,
Em = 541 nm; 2, Ex = 485 nm; and 3, Ex = 317 nm).

M. Yin, J. Sun / Journal of Alloys and Compounds 381 (2004) 50–57
[5] S. Wang, Z. Pang, K.D.L. Smith, M.J. Wagner, J. Chem. Soc., Dalton [14] J.H. Burns, W.H. Baldwin, Inorg. Chem. 16 (2) (1977) 289.
57
Trans. (1994) 955.
[6] B. Barja, R. Baggio, M.T. Garland, P.F. Aramendia, O. Peña, M.
Perec, Inorg. Chim. Acta 346 (2003) 187.
[7] X. Li, X. Zheng, L. Jin, S. Lu, J. Zhang, J. Mol. Struct. 559 (2001)
341.
[15] J.F. Ma, Z.S. Jin, J.Z. Ni, Chin. J. Struct. Chem. 10 (2) (1991)
125.
[16] W. Brzyska, A. Kula, J. Therm. Anal. 34 (1988) 899.
[17] H.Y. Zeng, Y.S. Yang, S.H. Huang, Chin. J. Lumin. 16 (4) (1995)
354.
[8] X. Li, L. Jin, S. Lu, J. Zhang, J. Mol. Struct. 604 (2002) 65.
[9] A.W.H. Lam, W.T. Wong, S. Gao, G. Wen, X.X. Zhang, Eur. J.
Inorg. Chem. (2003) 149.
[10] C. Seward, N.X. Hu, S. Wang, J. Chem. Soc., Dalton Trans. (2001)
134.
[11] X. Li, X. Zheng, L. Jin, S. Lu, W. Qin, J. Mol. Struct. 519 (2000) 85.
[12] X. Li, L. Jin, X. Zhang, S. Lu, J. Zhang, J. Mol. Struct. 607 (2002)
59.
[13] G.M. Sheldrick, SHELX-97, Program for X-ray Crystal Structure
Solution and Refinement, Göttingen University, Germany, 1997.
[18] M.C. Yin, L.J. Yuan, C.C. Ai, C.W. Wang, E.T. Yuan, J.T. Sun,
Polyhedron 23 (2004) 529.
[19] L.J. Yuan, M.C. Yin, E.T. Yuan, J.T. Sun, K.L. Zhang, Inorg. Chim.
Acta 357 (2004) 89.
[20] J.T. Sun, W. Xie, L.J. Yuan, K.L. Zhang, Q.Y. Wang, Mater. Sci.
Eng. B64 (1999) 157.
[21] P.C.R. Soares-Santos, H.I.S. Nogueira, J. Rocha, V. Félix, M.G.B.
Drew, R.A.S. Ferreira, L.D. Carlos, T. Trindade, Polyhedron 22
(2003) 3529.