Inorg. Chem.

2006, 45, 2857−2865

Structures, Photoluminescence, Up-Conversion, and Magnetism of 2D

and 3D Rare-Earth Coordination Polymers with Multicarboxylate
Linkages
Jin Yang, Qi Yue, Guo-Dong Li, Jun-Jun Cao, Guang-Hua Li, and Jie-Sheng Chen*

State Key Laboratory of Inorganic Synthesis and PreparatiVe Chemistry, College of Chemistry,
Jilin UniVersity, Changchun 130012, People’s Republic of China

Received September 12, 2005

Four new rare-earth compounds, [Eu(NDC)1.5(DMF)2] (1), [Nd2(NDC)3(DMF)4]‚H2O (2), [La2(NDC)3(DMF)4]‚0.5H2O

(3), and [Eu(BTC)(H2O)] (4), where NDC ) 1,4-naphthalenedicarboxylate, BTC ) 1,3,5-benzenetricarboxylate,
and DMF ) N,N-dimethylformamide, have been synthesized through preheating and cooling-down crystallization.
Compounds 1−3 possess similar 2D structures, in which the NDC ligands link MIII (M ) La, Nd, and Eu) ions of
two adjacent double chains constructed by NDC ligands and dinuclear MIII building units. In compound 4, the EuIII
ion is seven-coordinated by O atoms from six BTC ligands and one terminal water molecule in a distorted pentagonal-
bipyramidal coordination environment. If the BTC ligand and the EuIII ion are regarded as six-connected nodes,
respectively, the structure of compound 4 can be well described as a 3D six-connected net. Furthermore, compounds
1 and 4 exhibit strong red luminescence upon 355-nm excitation. Compound 2 displays interesting emissions in
the near-IR region, and yellow (580 nm) pumping of this compound results in UV and intense blue emissions
through an up-conversion process. The magnetic properties of compounds 1, 2, and 4 have been studied through
measurement of their magnetic susceptibilities over the temperature range of 4−300 K.

Introduction complexes usually exhibit intense luminescence and are

potentially applicable for the manufacture of fluorescent
Recently, 4f and 5f metal coordination compounds have probes and electroluminescent devices.5 The optical proper-
attracted increasing attention because of their interesting ties of lanthanide ions are different from those of other metal
properties such as magnetism,1 photoluminescence,2 photo-
ions and molecular species because they absorb and emit
voltaic conversion,3 and photocatalysis.4 Lanthanide (4f)
light over narrow wavelength ranges with high quantum
yields.6 Among the lanthanide ions, EuIII and NdIII are two
* To whom correspondence should be addressed. E-mail:
[email protected]. Tel.: +86-431-5168662. Fax: +86-431-5168624. of the most important luminescent centers. EuIII complexes
(1) (a) Yue, Q.; Yang, J.; Li, G. H.; Li, G. D.; Xu, W.; Chen, J. S.; Wang, have been regarded as attractive for use as visible lumines-
S. N. Inorg. Chem. 2005, 44, 5241. (b) Zheng, X. J.; Jin, L. P.; Gao,
S. Inorg. Chem. 2004, 43, 1600. (c) Kido, T.; Ikuta, Y.; Sunatsuki,
cent materials because of their strong red emissions (615
Y.; Ogawa, Y.; Matsumoto, N.; Re, N. Inorg. Chem. 2003, 42, 398. nm), while NdIII complexes emitting in the near-IR region
(d) Ma, B. Q.; Zhang, D. S.; Gao, S.; Jin, T. Z.; Yan, C. H.; Xu, G. (800-1700 nm) are the most popular near-IR luminescent
X. Angew. Chem., Int. Ed. 2000, 39, 3644.
(2) (a) Yu, Z. T.; Li, G. H.; Jiang, Y. S.; Xu, J. J.; Chen, J. S. J. Chem compounds for application in laser systems.7 Another
Soc., Dalton Trans. 2003, 22, 4219. (b) Bassett, A. P.; Magennis, S. interesting feature of NdIII compounds is their frequency up-
W.; Glover, P. B.; Lewis, D. J.; Spencer, N.; Parsons, S.; Williams,
R. M.; Cola, L. D.; Pikramenou, Z. J. Am. Chem. Soc. 2004, 126, conversion of IR radiation into the visible region, and thus
9413. (c) Reineke, T. M.; Eddaoudi, M.; Fehr, M.; Kelley, D.; Yaghi, NdIII-containing complexes may also find application in two-
O. M. J. Am. Chem. Soc. 1999, 121, 1651. (d) Serre, C.; Stock, N.;
Bein, T.; Férey, G. Inorg. Chem. 2004, 43, 3159. (e) Vicentini, G.;
Zinner, L. B.; Zukerman-Schpector, J.; Zinner, K. Coord. Chem. ReV. (5) (a) Buünzli, G. J. C.; Piguet, C. Chem. ReV. 2002, 102, 1897. (b)
2000, 196, 353. Tsukube, H.; Shinoda, S. Chem. ReV. 2002, 102, 2389. (c) Capecchi,
(3) Chen, W.; Yuan, H. M.; Wang, J. Y.; Liu, Z. Y.; Yang, M. Y.; Chen, S.; Renault, O.; Moon, D. G.; Halim, M.; Etchells, M.; Dobson, P. J.;
J. S. J. Am. Chem. Soc. 2003, 125, 9266. Salata, O. V.; Christou, V. AdV. Mater. 2000, 12, 1591. (d) Kido, J.;
(4) (a) Yu, Z. T.; Liao, Z. L.; Jiang, Y. S.; Li, G. H.; Chen, J. S. Chem.s Okamoto, Y. Chem. ReV. 2002, 102, 2357.
Eur. J. 2005, 11, 2642. (b) Yu, Z. T.; Liao, Z. L.; Jiang, Y. S.; Li, G. (6) Sabbatini, N.; Guardigli, M.; Lehn, J. M. Coord. Chem. ReV. 1993,
H.; Li, G. D.; Chen, J. S. Chem Commun. 2004, 1814. 123, 201.

10.1021/ic051557o CCC: $33.50 © 2006 American Chemical Society Inorganic Chemistry, Vol. 45, No. 7, 2006 2857
Published on Web 03/01/2006
 Yang et al.
photon fluorescence imaging.8
Nevertheless, the photophysi- magnetic behaviors of these compounds have also been
cal properties of lanthanide complexes markedly depend on investigated.
their structures, and therefore it is of great significance to
obtain new structures of rare-earth compounds and to reveal Experimental Section
the relationship between the structures and photophysical Materials. EuCl3‚6H2O, NdCl3‚6H2O, and LaCl3‚6H2O were
properties for these compounds.9 In all types of rare-earth prepared by dissolving Eu2O3, Nd2O3, and La2O3, respectively, in
compounds, carboxylate anions with aromatic rings are hydrochloric acid followed by drying and crystallization. The H2-
widely used in the construction of high-dimensional lan- NDC, H3BTC, and other reagents of analytical grade were
thanide coordination polymers because these anions are able purchased commercially and used without further purification.
to act as bridging ligands in various ligating modes.10 Synthesis of [Eu(NDC)1.5(DMF)2] (1). EuCl3‚6H2O (0.122 g,
Conventionally, the syntheses of rare-earth carboxylate 0.33 mmol) and H2NDC (0.108 g, 0.5 mmol) were dissolved in
compounds are carried out in aqueous media, where water DMF (10 mL). The resulting mixture was stirred for about 1 h at
room temperature, sealed in a 23-mL Teflon-lined stainless steel
molecules easily coordinate to the rare-earth centers and
autoclave, and heated at 80 °C for 3 days under autogenous pressure.
usually quench the luminescence intensity.11 Moreover, Afterward, the reaction system was gradually cooled to room
aromatic carboxylic acids show low solubility in aqueous temperature at a rate of 15 °C h-1. Colorless crystals of 1 suitable
solution even under hydrothermal conditions because of the for single-crystal X-ray diffraction (XRD) analysis were collected
presence of conjugated aromatic rings, leading to difficulty from the final reaction system by filtration, washed several times
in obtaining single crystals of rare-earth carboxylate materi- with DMF, and dried in air at ambient temperature. Yield: 45%
als. To obtain single crystals of lanthanide aromatic car- based on EuIII. Elem and ICP anal. Calcd for C24H22EuN2O8: C,
boxylate complexes, we tried an unconventional synthetic 46.61; H, 3.59; N, 4.53; Eu, 24.57. Found: C, 46.33; H, 3.83; N,
approach in which N,N-dimethylformamide (DMF) was used 4.91; Eu, 24.81. IR (cm-1): 2944 (w), 1656 (s), 1597 (m), 1474
as the solvent and the crystallization was realized through a (m), 1422 (s), 1364 (s), 1267 (w), 1106 (w), 846 (s), 794 (m), 678
(w), 568 (w), 438 (m).
preheating and cooling-down route. We chose 1,4-naphtha-
Synthesis of [Nd2(NDC)3(DMF)4]‚H2O (2). Compound 2 was
lenedicarboxylate (NDC) and 1,3,5-benzenetricarboxylate
prepared in the same way as that for 1 but using NdCl3‚6H2O (0.120
(BTC) as linkers and chelating ligands to coordinate to the g, 0.33 mmol) and H2NDC (0.108 g, 0.5 mmol) as the reactants.
rare-earth metals. Both the rodlike NDC and the starlike BTC Rose-colored crystals were obtained in a 43% yield based on NdIII.
molecules possess interesting features that are conducive to Elem and ICP anal. Calcd for C48H48N4Nd2O17: C, 46.44; H, 3.90;
the formation of versatile coordination structures.10a First, N, 4.51; Nd, 23.24. Found: C, 46.17; H, 3.66; N, 4.72; Nd, 23.43.
the multicarboxylate groups on the molecules may be IR (cm-1): 3423 (w), 2931 (w), 1653 (s), 1594 (m), 1476 (m),
completely or partially deprotonated and, second, the car- 1423 (s), 1364 (s), 1266 (w), 1104 (w), 846 (s), 792 (m), 681 (w),
boxylate groups may not lie in the phenyl ring plane upon 566 (w), 435 (m).
coordination to metal ions owing to space hindrance, and as Synthesis of [La2(NDC)3(DMF)4]‚0.5H2O (3). Compound 3 was
a result, the molecules may connect metal ions in different prepared similarly, using LaCl3‚6H2O (0.118 g, 0.33 mmol) and
directions. In this paper, we describe the successful synthesis H2NDC (0.108 g, 0.5 mmol) as the reactants. Colorless crystals
were obtained in a 56% yield based on LaIII. Elem and ICP anal.
of four new lanthanide compounds with extended structures,
Calcd for C48H47La2N4O16.5: C, 47.19; H, 3.88; N, 4.59; La, 22.74.
[Eu(NDC)1.5(DMF)2] (1), [Nd2(NDC)3(DMF)4]‚H2O (2), Found: C, 46.89; H, 3.56; N, 4.23; La, 22.96. IR (cm-1): 3427
[La2(NDC)3(DMF)4]‚0.5H2O (3), and [Eu(BTC)(H2O)] (4) (w), 2933 (w), 1657 (s), 1593 (m), 1474 (m), 1421 (s), 1365 (s),
in the presence of DMF as the solvent, through the preheating 1266 (w), 1106 (w), 845 (s), 792 (m), 680 (w), 569 (w), 439 (m).
and cooling-down crystallization approach. The photolumi- Synthesis of [Eu(BTC)(H2O)] (4). EuCl3‚6H2O (0.122 g, 0.33
nescence, up-conversion property, and temperature-dependent mmol) and H3BTC (0.070 g, 0.33 mmol) were dissolved in DMF
(10 mL). The resulting solution was stirred for about 1 h at room
(7) (a) Beeby, A.; Faulkner, S. Chem. Phys. Lett. 1997, 266, 116. (b) temperature, sealed in a 23-mL Teflon-lined stainless steel auto-
Imbert, D.; Cantuel, M.; Bünzli, J. C. G.; Bernardinelli, G.; Piguet, clave, and heated at 85 °C for 5 days under autogenous pressure.
C. J. Am. Chem. Soc. 2003, 125, 15698. (c) Weber, M. J. In Lanthanide Afterward, the reaction system was gradually cooled to room
and Actinide Chemistry and Spectroscopy; Edelstein, N. M., Ed.; ACS
Symposium Series 131; American Chemical Society: Washington, temperature at a rate of 15 °C h-1. Colorless crystals of 4 suitable
DC, 1980; p 275. (d) Ryo, M.; Wada, Y.; Okubo, T.; Hasegawa, Y.; for single-crystal XRD analysis were collected from the final
Yanagida, S. J. Phys. Chem. B 2003, 107, 11302. reaction system by filtration and dried in air at ambient temperature.
(8) (a) Patra, A.; Friend, C. S.; Kapoor, R.; Prasad, P. N. Chem. Mater.
2003, 15, 3650. (b) Wang, X.; Kong, X.; Shan, G.; Yu, Y.; Sun, Y.; Yield: 39% based on EuIII. Elem and ICP anal. Calcd for C4.5H2.5-
Feng, L.; Chao, K.; Lu, S.; Li, Y. J. Phys. Chem. B 2004, 108, 18408. Eu0.5O3.5: C, 28.67; H, 1.34; Eu, 40.30. Found: C, 28.92; H, 1.19;
(9) Deun, R. V.; Fias, P.; Nockemann, P.; Schepers, A.; Parac-Vogt, T. Eu, 40.91. IR (cm-1): 3397 (m), 2769 (w), 1616 (s), 1559 (s), 1442
N.; Hecke, K. V.; Meervelt, L. V.; Binnemans, K. Inorg. Chem. 2004,
43, 8461.
(m), 1369 (s), 1111 (w), 769 (m), 704 (w), 529 (w).
(10) (a) Wang, Z.; Kravtsov, V. C.; Zaworotko, M. J. Angew. Chem., Int. General Characterization and Physical Measurements. The
Ed. 2005, 44, 2. (b) Lin, Z.; Jiang, F.; Chen, L.; Yuan, D.; Hong, M. IR spectra were recorded within the 400-4000-cm-1 region on a
Inorg. Chem. 2005, 44, 73. (c) Zheng, X.-J.; Jin, L. P.; Gao, S.; Lu,
S. Z. New J. Chem. 2005, 6, 798. (d) Rosi, N. L.; Kim, J.; Eddaoudi, Bruker IFS 66V/S Fourier transform IR (FTIR) spectrometer using
M.; Chen, B.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2005, KBr pellets. The C, H, and N elemental analysis was conducted
127, 1504. (e) Kim, Y. J.; Jung, D. Y. Chem. Commun. 2002, 908. (f) on a Perkin-Elmer 240C element analyzer, whereas the inductively
Ghosh, S. K.; Bharadwaj, P. K. Inorg. Chem. 2004, 43, 2293. (g) coupled plasma (ICP) analysis was performed on a Perkin-Elmer
Ghosh, S. K.; Bharadwaj, P. K. Inorg. Chem. 2003, 42, 8250.
(11) Bellusci, A.; Barberio, G.; Crispini, A.; Ghedini, M.; Deda, M. L.; Optima 3300DV ICP spectrometer. The powder XRD data were
Pucci, D. Inorg. Chem. 2005, 44, 1818. collected on a Siemens D5005 diffractometer with Cu KR radiation

2858 Inorganic Chemistry, Vol. 45, No. 7, 2006

2D and 3D Rare-Earth Coordination Polymers

Table 1. Crystallographic Data for Complexes 1-4

1 2 3 4
empirical formula C24H22EuN2O8 C48H48N4Nd2O17 C48H47La2N4O16.5 C4.5H2.5Eu0.5O3.5
fw 618.40 1241.38 1221.72 188.55
space group P1h P1h P1h P4322
a [Å] 11.3894(13) 11.465(2) 11.5541(9) 10.3627(15)
b [Å] 11.5985(18) 11.704(2) 11.7802(10) 10.3627(15)
c [Å] 11.7351(17) 23.342(5) 23.5745(15) 14.332(3)
R [deg] 77.968(10) 79.08(3) 79.366(5) 90
β [deg] 61.694(8) 87.29(3) 87.169(5) 90
γ [deg] 86.258(9) 62.07(3) 62.000(5) 90
V [Å3] 1333.8(3) 2714.2(9) 2781.9(4) 1539.1(4)
Z 2 2 2 8
F [g cm-3] 1.540 1.519 1.459 1.627
µ [mm-1] 2.397 1.961 1.581 4.089
GOF on F 2 0.906 1.078 0.915 0.953
R [I > 2σ(I)]a R1 ) 0.0601 R1 ) 0.0512 R1 ) 0.0518 R1 ) 0.0404
wR2 ) 0.1117 wR2 ) 0.1536 wR2 ) 0.1019 wR2 ) 0.0904
a R1 ) ∑||Fo| - |Fc||/∑ |Fo|; wR2 ) {∑[w(Fo2 - Fc2)2]/∑[w(Fo2)]2}1/2.

(λ ) 1.5418 Å), and the recording speed was 0.3° min-1 over the The structures of compounds 2 and 3 are similar to that of
2θ range of 4-40° at room temperature. The simulated and compound 1, and therefore only the structures of 1 and 4
experimental powder XRD patterns of compounds 1-4 are shown will be described in detail. The experimental powder XRD
in the Supporting Information (Figures S5-S8). Temperature- and elemental and ICP analyses of compounds 1-4 were
dependent magnetic susceptibility data for polycrystalline com-
performed before their properties were measured. The
pounds 1, 2, and 4 were obtained on a Quantum Design MPMS-
XL SQUID magnetometer under an applied field of 1000 Oe over elemental and ICP analysis results for all of the compounds
the temperature range of 4-300 K. The visible luminescent well correspond to the data calculated from the single-crystal
properties of compounds 1 and 4 were measured on a Perkin-Elmer structure formulas (see the Experimental Section). The
LS55 spectrometer. The near-IR emission spectrum of compound experimental powder XRD patterns are also in good agree-
2 was recorded on an Edinburgh Analytical Instruments FLS920 ment with the corresponding simulated ones (Figures S5-
equipped with a laser diode from the PicoQuant Company as the S8 in the Supporting Information) except for the relative
light source, whereas the up-conversion spectrum of this compound intensity variation because of preferred orientations of the
was obtained using a tunable pulsed laser (Continuum Sunlite OPO). crystals. Therefore, the phase purity of the as-synthesized
The luminescent lifetime was measured with a TR550 (J-Y
products is substantiated.
Company) upon excitation with a Nd:YAG laser.
X-ray Crystallography. Crystallographic data of compounds 2 Structural Description of 1. The asymmetric unit for
and 4 were collected on a Rigaku RAXIS-RAPID single-crystal compound 1 is shown in Figure 1a. It is seen that each EuIII
diffractometer equipped with a narrow-focus, 5.4-kW sealed-tube center is coordinated by nine O atoms from six NDC anions
X-ray source (graphite-monochromated Mo KR radiation with λ (O1, O2, O5, O4A, O3A, O3B, and O6A) and two DMF
) 0.710 73 Å) at a temperature of 20 ( 2 °C. The data processing molecules (O7 and O8). The Eu-O(carboxylate) bond
was accomplished with the PROCESS-AUTO processing program. distances ranging from 2.371 to 2.654 Å and the Eu-
Crystallographic data for 1 and 3 were recorded at room temperature O(DMF) bond distances from 2.447 to 2.460 Å are similar
on a Bruker-AXS Smart CCD diffractometer equipped with a to previously reported Eu-O lengths.14 It is well-known that
normal-focus, 2.4-kW X-ray source (graphite-monochromated Mo
the two possible ground-state geometries for a nine-coordina-
KR radiation with λ ) 0.710 73 Å) operating at 50 kV and 40 mA
with increasing ω (width of 0.3° and exposure time of 30 s frame-1). tion polyhedron are the symmetrical tricapped trigonal prism
All of the structures were solved by direct methods using the with D3h symmetry and the monocapped square antiprism
program SHELXS-9712 and refined by full-matrix least-squares with C4V symmetry.15 The polyhedron of the EuIII coordina-
techniques against F2 using the SHELXTL-9713 crystallographic tion sphere for compound 1 is best described as a distorted
software package. All non-H atoms were easily found from the tricapped trigonal prism (Figure 1b).
difference Fourier map and refined anisotropically, whereas the H In compound 1, the NDC anions display two orientations,
atoms of the organic molecules were placed by geometrical
and the dihedral angle between the naphthalene rings of the
considerations and were added to the structure factor calculation.
two oriented NDC molecules is 159.5°. For convenience,
The detailed crystallographic data and structure refinement param-
eters for 1-4 are summarized in Table 1. the NDC anions containing the O atoms labeled O1 and O5
(Figure 1a) are designated as NDC1 and NDC2, respectively.
Results and Discussion In coordination mode 1 (for NDC1), one carboxylate moiety
chelates one EuIII ion, while the other carboxylate group links
Selected bond distances and angles for compounds 1-4
are listed in Tables S1-S4 (see the Supporting Information).
(14) (a) Li, J. R.; Bu, X. H.; Zhang, R. H.; Duan, C. Y.; Wong, K. M. C.;
Yam, V. W. W. New J. Chem. 2004, 28, 261. (b) Bu, X.-H.; Weng,
(12) Sheldrick, G. M. SHELXS-97, Programs for X-ray Crystal Structure W.; Du, M.; Chen, W.; Li, J.-R.; Zhang, R.-H.; Zhao, L.-J. Inorg.
Solution; University of Göttingen: Göttingen, Germany, 1997. Chem. 2002, 41, 1007.
(13) Sheldrick, G. M. SHELXL-97, Programs for X-ray Crystal Structure (15) Hou, H.; Wei, Y.; Song, Y.; Fan, Y.; Zhu, Y. Inorg. Chem. 2004, 43,
Refinement; University of Göttingen: Göttingen, Germany, 1997. 1323.

Inorganic Chemistry, Vol. 45, No. 7, 2006 2859

 Yang et al.

Figure 2. 2D network structure of 1 viewed along the c axis.

Figure 1. View of the asymmetric unit of compound 1 (all H atoms are

omitted for clarity) (a) and the distorted tricapped trigonal-prismatic
coordination polyhedron of the EuIII ion (b).

Chart 1. Coordination Modes of the NDC and BTC Molecules in

Compounds 1-4

Figure 3. View of the asymmetric unit of compound 4 (all H atoms are

omitted for clarity) (a) and the distorted pentagonal-bipyramidal coordination
three EuIIIions. In mode 2 (for NDC2), each carboxylate sphere of the EuIII ion (b).
moiety bridges two adjacent EuIII ions (Chart 1).
The dinuclear EuIII units in compound 1 are further angles for compounds 1-3 are observed to vary from
connected through NDC ligands, resulting in a unique 2D compound to compound because the radii of MIII (M ) La,
layer network. First, the NDC1 ligands link the dimer units Nd, and Eu) are in the order 1 < 2 < 3. In addition, whereas
to form 1D double-chain structures (Figure 2), and the compound 1 is completely water-free, compounds 2 and 3
distance between adjacent dimer units in the chain is 12.25 contain water molecules occluded in the voids of the
Å. Second, the NDC2 ligands link the EuIII units of two structural networks. It is believed that these water molecules
adjacent chains to form the 2D layers (Figure 2). Moreover, originate from the starting reactants NdCl3‚6H2O and LaCl3‚
the layers are packed in a parallel fashion to form a 3D 6H2O. Nevertheless, they are not coordinated to the metal
supramolecular structure through π-π interactions of adja- ions of the final products in the presence of DMF as the
cent naphthalene rings. predominant solvent in the reaction system.
The structures of compounds 2 and 3 are similar to that Structural Description of 4. The asymmetric unit for
of compound 1. Nevertheless, a small difference exists for compound 4 is shown in Figure 3a. Each EuIII ion in 4 is
these three compounds. As shown in Tables S1-S4 (see the seven-coordinated by O atoms from six BTC ligands (O1,
Supporting Information), the metal-O bond distances and O1B, O2B, O2C, O3B, and O3C) and one terminal water
2860 Inorganic Chemistry, Vol. 45, No. 7, 2006
2D and 3D Rare-Earth Coordination Polymers

molecule (Ow1) in a distorted pentagonal-bipyramidal

coordination sphere, in which the four O atoms from four
BTC anions (O2B, O2C, O3B, and O3C) and one O atom
from the water molecule (Ow1) make up the basal plane,
while the axial positions are occupied by two O atoms (O1
and O1B) from another two BTC molecules (Figure 3b). The
Eu-O(carboxylate) bond lengths vary from 2.321 to 2.369
Å, and the Eu-Ow1 distance is 2.469 Å. The O-EuIII-O
bond angles range from 69 to 161.3°.
The interesting feature of compound 4 is the presence of
helical strands in the structure. As depicted in Figure 4, the
BTC ligands bridge adjacent EuIII ions to form three-stranded
helical chains running along the crystallographic 43 axis. The
occurrence of helical strands in compound 4 is attributable
to the steric orientation of the carboxylate groups of BTC.
The helical chains are further linked with each other through
the BTC ligands to form a 3D framework. In addition, unlike
the previously reported 3D Eu3(H2O)(OH)6(BTC)3‚3H2O
compound whose structure consists of [Eu3(OH)6]n sheets
linked together by BTC ligands,16 compound 4 is composed
of mononuclear EuIII cations bridged by BTC ligands in all
three directions. Each carboxylate group in 4 connects two
EuIII ions in a bidentate manner, and each ligand bridges six
adjacent EuIII ions through their carboxylate O atoms. Thus,
if the BTC ligand and the seven-coordinated EuIII ion are
regarded as the six-connected nodes, the framework topology
of compound 4 can be regarded as of the 3D six-connected
net.17 This observation suggests that the flexible coordination
mode of the BTC ligand in combination with the high
coordination number of EuIII favors the formation of a highly
connected net.
It is worthwhile to note that, although the DMF molecules
do not coordinate to the EuIII ions in compound 4, they play
an important role in the crystallization process of the
compound. In the absence of DMF, no crystals of compound
4 were obtained under similar synthetic conditions. The
presence of DMF improves the solubility of the ligands and
makes the crystal growth more homogeneous.
Photoluminescence. The solid-state photoluminescent
spectra of compounds 1, 2, and 4 were recorded at room
temperature. As shown in Figure 5a, the NDC ligand exhibits
a fluorescent emission band at 472 nm (λex ) 392 nm), while
the free BTC ligand shows an emission band at 380 nm (λex
) 334 nm). The emission bands for these two free ligands
are attributable to the π* f n transitions.18 Compound 3
contains a nonemissive LaIII ion, and this material shows a
very weak emission band at 533 nm (λex ) 392 nm), which
is believed to arise from charge-transfer transition between
the NDC ligand and the central LaIII ion.18 The photolumi-
nescent spectra of compounds 1, 2, and 4 exhibit emission Figure 4. 3D framework structure of 4 viewed along the c axis (a), the
three-stranded helical structure running along the crystallographic 43 axis
(b), and the 3D structure of 4 viewed along the a axis (c).
(16) Serre, C.; Férey, G. J. Mater. Chem. 2002, 12, 3053.
(17) (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460.
(b) Chen, X. Y.; Zhao, B.; Shi, W.; Xia, J.; Cheng, P.; Liao, D. Z.; bands characteristic of the corresponding luminescent lan-
Yan, S. P.; Jiang, Z. H. Chem. Mater. 2005, 17, 2866. (c) Ma, J. F.; thanide ions, whereas the emissions arising from the free
Yang, J.; Zheng, G. L.; Li, L.; Liu, J. F. Inorg. Chem. 2003, 42, 7531.
(18) (a) Chen, W.; Wang, J. Y.; Chen, C.; Yue, Q.; Yuan, H. M.; Chen, J. ligands are not observable for these three compounds. The
S.; Wang, S. N. Inorg. Chem. 2003, 42, 944. (b) Wang, X.; Qin, C.; absence of ligand-based emission suggests energy transfer
Wang, E.; Li, Y.; Hao, N.; Hu, C.; Xu, L. Inorg. Chem. 2004, 43,
1850. (c) Sun, Y.-Q.; Zhang, J.; Chen, Y.-M.; Yang, G.-Y. Angew. from the ligands to the lanthanide center during photolumi-
Chem., Int. Ed. 2005, 44, 5814. nescence.18c Compounds 1 and 4 (both contain EuIII ions)

Inorganic Chemistry, Vol. 45, No. 7, 2006 2861

 Yang et al.
5 7
emission D0 f F0 at 568 nm can be found for solid 4. It
is well-known that the transition 5D0 f 7F0 is strictly
forbidden in a field of high symmetry and, therefore, the
EuIII ion in 4 should occupy sites with a low symmetry and
no inversion center should be present for these sites, in
agreement with the crystal structural analysis.2e,20 The 5D0
f 7F1 transition (593 nm for 1 and 592 nm for 4) corresponds
to a magnetic dipole transition, and the intensities of this
emission for both 1 and 4 are medium-strong. The most
intense emissions in the luminescent spectra are the 5D0 f
7
F2 transitions at 618 and 617 nm for 1 and 4, respectively,
which are the so-called hypersensitive transitions and are
responsible for the brilliant-red emission of these com-
plexes.21 The 5D0 f 7F3 transition at 641 nm is observed for
4, whereas it is nearly invisible for compound 1. Compound
2 has no emission in the visible region. However, this
material shows distinct emissions in the near-IR region
(Figure 5c). Near-IR-emitting materials based on rare-earth
compounds have attracted considerable attention recently
because they are promising candidates for active components
in near-IR-luminescent optical devices.22 The profiles of the
emission bands for 2 are in agreement with previously
reported spectra of NdIII complexes.23 Under an excitation
of 488 nm, compound 2 displays a strong emission band at
1059 nm (4F3/2 f 4I11/2), an emission band at 893 nm (4F3/2
f 4I9/2) with a much lower intensity, and a very weak band
at 1333 nm (4F3/2 f 4I13/2).23
The luminescence decay curves of complexes 1 and 4 were
obtained at room temperature. The decay curves are well
fitted into a single-exponential function as I ) I0 exp(-t/τ),
where I and I0 are the luminescent intensities at times t and
0 and τ is defined as the luminescent lifetime, indicating
that all of the EuIII ions occupy the same average local
environment.24 As shown in Figure 6, the luminescence
lifetimes of compounds 1 and 4 are slightly different. The
one for 1 is about 1.0 ms (Figure 6a), whereas that for 2 is
about 0.84 ms (Figure 6b). This difference in lifetimes for
the two compounds may result from the presence of

(20) (a) Kim, Y. J.; Suh, M.; Jung, D. Y. Inorg. Chem. 2004, 43, 245. (b)
Serre, C.; Pelle, F.; Gardant, N.; Férey, G. Chem. Mater. 2004, 16,
1177.
(21) (a) de Bettencourt-Dias, A. Inorg. Chem. 2005, 44, 2737. (b) Law, G.
L.; Wong, K. L.; Zhou, X.; Wong, W. T.; Tanner, P. A. Inorg. Chem.
2005, 44, 4142.
(22) (a) Curry, R. J.; Gillin, W. P. Appl. Phys. Lett. 1999, 75, 1380. (b)
Curry, R. J.; Gillin, W. P.; Knights, A. P.; Gwilliam, R. Appl. Phys.
Figure 5. Solid-state emission spectra for a free NDC ligand excited at
Lett. 2000, 77, 2271. (c) Khreis, O. M.; Curry, R. J.; Somerton, M.;
392 nm, the BTC ligand excited at 334 nm, and compound 3 excited at Gillin, W. P. J. Appl. Phys. 2000, 88, 777. (d) Guo, X.; Zhu, G.; Fang,
392 nm (a), for 1 excited at 355 nm, for 4 excited at 355 nm (b), and for Q.; Xue, M.; Tian, G.; Sun, J.; Li, X.; Qiu, S. Inorg. Chem. 2005, 44,
2 excited at 488 nm (c). All of the spectra were recorded at room 3850.
temperature. (23) (a) Castro, A.; Enjalbert, R.; Lloyd, D.; Rasines, I.; Galy, J. J. Solid
State Chem. 1990, 85, 100. (b) Tarasov, I. V.; Dolgikh, V. A.;
emit red light upon excitation at 355 nm, and their lumi- Aksel’rud, L. G.; Berdonosov, P. S.; Ponovkin, B. A. Zh. Neorg. Khim.
nescence spectra are depicted in Figure 5b. These emission 1996, 41, 1243. (c) Nikiforov, G. B.; Kusainova, A. M.; Berdonosov,
P. S.; Dolgikh, V. A.; Lightfoot, P. J. Solid State Chem. 1999, 146,
bands arise from 5D0 f 7FJ (J ) 0-4) transitions, typical 473. (d) Berdonosov, P. S.; Charkin, D. O.; Kusainova, A. M.;
of EuIII ions.19 For 1, the 5D0 f 7F0 and 5D0 f 7F3 transitions Hervoches, C. H.; Dolgikh, V. A.; Lightfoot, P. Solid State Sci. 2000,
2, 553. (e) Song, J. L.; Mao, J. G. Chem.sEur. J. 2005, 11, 1417.
are too weak to be observed, but the symmetry-forbidden (24) (a) Ma, J.-F.; Yang, J.; Li, S.-L.; Song, S.-Y.; Zhang, H.-J.; Wang,
H.-S.; Yang, K.-Y. Cryst. Growth Des. 2005, 5, 807. (b) Pang, X.;
(19) (a) Lenaerts, P.; Driesen, K.; Deun, R. V.; Binnemans, K. Chem. Mater. Sun, H.; Zhang, Y.; Shen, Q.; Zhang, H. Eur. J. Inorg. Chem. 2005,
2005, 17, 2148. (b) He, Z.; Gao, E. Q.; Wang, Z. M.; Yan, C. H.; 1487. (c) Choppin, G. R.; Peterman, D. R. Coord. Chem. ReV. 1998,
Kurmoo, M. Inorg. Chem. 2005, 44, 862. (c) Wang, Y.; Zheng, X.; 174, 283. (d) Bartelemy, P. P.; Choppin, G. R. Inorg. Chem. 1989,
Zhuang, W.; Jin, L. Eur. J. Inorg. Chem. 2003, 3572. 28, 3354.

2862 Inorganic Chemistry, Vol. 45, No. 7, 2006

2D and 3D Rare-Earth Coordination Polymers

Figure 7. Up-conversion fluorescence spectrum of compound 2 recorded

at room temperature (580-nm excitation).

Figure 6. Luminescence decay curves for compound 1 (λex ) 355 nm;

λem ) 618 nm) (a) and for compound 4 (λex ) 355 nm; λem ) 617 nm) (b).

coordinating water molecules in 4, the vibration of which

can effectively remove the electronic energy of excited EuIII
ions.24
Up-Conversion Property. Since the early reviews by
Auzel and Wright about up-conversion processes, there has
been extensive interest in up-conversion processes, up-
conversion materials, and up-conversion applications,25 and
the search for new up-conversion compounds is one of the
fundamental studies. Rare-earth-containing compounds have
been found to be promising materials for up-conversion Figure 8. Schematic representation of two fundamental up-conversion
mechanisms.
applications. However, most of the up-conversion rare-earth
materials reported so far involve no organic ligands, and Figure 8 schematically shows the two most important up-
the use of LnIII coordination polymers as up-conversion conversion mechanisms in a simple three-level picture.28 In
compounds has rarely appeared in the literature.26 Therefore, Figure 8a, the emitting state is reached by a sequence of
it is highly desirable to explore the up-conversion properties ground-state absorption (GSA) and excited-state absorption
of the rare-earth compounds we synthesized. Among com- (ESA) steps. In this process (GSA/ESA), two photons are
pounds 1-4, 2 contains NdIII species, and this material successively absorbed by one metal ion, and this mechanism
exhibits interesting up-conversion emissions (Figure 7). A is well documented for LnIII-doped crystals and glasses.29
weak UV up-conversion emission at about 391.6 nm and Energy-transfer up-conversion (ETU) or GSA/ETU involves
a much stronger blue emission at about 449.5 nm show up two ions in close proximity, and two metal ions are excited
for 2 upon pulse laser excitation at 580 nm. The reason by GSA to their respective metastable intermediate states
behind the selection of the 580-nm excitation wavelength (Figure 8b).30 This is followed by a nonradiative energy-
is that NdIII compounds have intense absorption at 580 nm transfer process resulting in one ion in the final excited state
corresponding to transition 4I9/2 f 4G5/2, which is a hyper- and the second one in the ground state. This mechanism is
sensitive band and satisfies the selection rules of ∆J ) (2, also well established in LnIII systems.31
∆L ) (2, and ∆S ) 0. Up-conversion emission peaks In the crystal structure of compound 2, the distance
at these two wavelengths have also been observed for between the dinuclear NdIII ions bridged by the carboxylate
the NdIII-doped Bi4Ge3O12 and Pb5Al3F19 crystals, respec- O atom is 4.101 Å, which enables facile energy transfer
tively.27 between two optically active NdIII ions, resulting in efficient

(25) (a) Auzel, F. Acad. Sci. Paris 1966, 1016. (b) Wright, J. C. Topics in (28) (a) Reinhard, C.; Valiente, R.; Güdel, H. U. J. Phys. Chem. B 2002,
Applied Physics: Radiationless Processes in Molecules and Condensed 106, 10051. (b) Gerner, P.; Wenger, O. S.; Valiente, R.; Güdel, H. U.
Phases; Fong, F. K., Ed.; Springer: Berlin, 1976; pp 239-295. (c) Inorg. Chem. 2001, 40, 4534.
Layne, B.; Lowdermilk, W. H.; Weber, M. J. Phys. ReV. B 1997, 16, (29) (a) Vetrone, F.; Boyer, J.-C.; Capobianco, J. A.; Speghini, A.; Bettinelli,
10. M. J. Phys. Chem. B 2003, 107, 10747. (b) Oomen, E. W. J. L. AdV.
(26) (a) Auzel, F. Chem. ReV. 2004, 104, 139. (b) Gamelin, D. R.; Güdel, Mater. 1991, 3, 403.
H. U. Acc. Chem. Res. 2000, 33, 235. (30) (a) Cockroft, N. J.; Jones, G. D.; Syme, R. W. G. J. Lumin. 1989, 43,
(27) (a) Ju, J. J.; Kwon, T. Y.; Kim, H. K.; Kim, J. H.; Kim, S. C.; Cha, 275. (b) Salley, G. M.; Valiente, R.; Güdel, H. U. J. Lumin. 2001,
M.; Yun, S. I. Mater. Lett. 1996, 29, 13. (b) Fernández, J.; Sanz, M.; 94-95, 305. (c) Gamelin, D. R.; Güdel, H. U. Inorg. Chem. 1999,
Mendioroz, A.; Balda, R.; Chaminade, J. P.; Ravez, J.; Lacha, L. M.; 38, 5154.
Voda, M.; Arriandiaga, M. A. J. Alloys Compd. 2001, 323-324, 267. (31) Auzel, F. Proc. IEEE 1973, 61, 758.

Inorganic Chemistry, Vol. 45, No. 7, 2006 2863

 Yang et al.
up-conversion through the GSA/ETU process.32
On the other
hand, because the NDC ligand shows no absorption at about
580 nm in the UV-vis spectrum (Figure S9 in the Supporting
Information), the excitation wavelength (580 nm) should
correspond to the 4I9/2 f 4G5/2 transition of the NdIII ions.27a
On the basis of the crystal structure, a GSA/ETU mechanism
is more likely for the up-conversion of our system.33
However, the possibility of the coexistence of GSA/ETU and
GSA/ESA mechanisms in the up-conversion process of 2
cannot be excluded yet.
Magnetic Properties. The temperature-dependent mag-
netic susceptibility data of compounds 1, 2, and 4 have been
measured for polycrystalline samples at an applied magnetic
field of 1000 Oe in the temperature range of 4-300 K. The
plots of χMT and 1/χM vs T of the three compounds 1, 2,
and 4 are shown in Figure 9. For 1, as the temperature is
lowered from room temperature, the χMT value decreases,
owing to the depopulation of the Stark levels with nonzero
J values for a single EuIII ion (Figure 9a). At the lowest
temperature, χMT is close to zero, indicative of a J ) 0
ground state of the EuIII ion (7F0).19b The magnetic suscep-
tibility above 200 K follows the Curie-Weiss law because
of the presence of thermally populated excited states.
In the experimental χMT vs T curve for 2, there is
a decrease in the value of χMT as the temperature is lowered
from room temperature to 4 K (Figure 9b). The occurrence
of this behavior is attributed to the contribution of the
crystal field, which splits the 4I9/2 free-ion ground state into
five Kramers doublets, interpreted by Kahn and co-workers
for the compound [NdL2(H2O)4](ClO4)3‚4H2O, where L
) 2-formyl-4-methyl-6-[N-(2-pyridylethyl)formimidoyl]-
phenol.34 Considering the large anisotropy of the NdIII sys-
tem, it is difficult to fit the magnetic data with an accurate
model. Nevertheless, in the 50-300 K temperature range,
the magnetic susceptibility data of 2 can be described by
a Curie-Weiss fitting with C ) 3.05 cm3 K mol-1 and θ
) -30.04 K. The large θ values indicate the importance
of ligand-field effects in compound 2. The nature of Figure 9. Plots of the temperature dependence of χMT (open squares)
the interactions between LnIII ions with a first-order orbi- and χM-1 (open circles) for compounds 1 (a), 2 (b), and 4 (c). The solid
tal momentum, such as NdIII ions, cannot simply be de- lines show the best fit to the Curie-Weiss law for 2 in the 50-300 K
temperature range.
duced from the shape of the χMT vs T curve and the θ value
alone.35
ity of the structures as well as the lack of suitable models,
For compound 4, again the χMT value continuously more detailed calculations of the magnetic interactions for
decreases to almost 0 as T approaches 0 K (Figure 9c), 1, 2, and 4 seem to be difficult.
mainly because of the depopulation of the Stark levels with
nonzero J values for a single EuIII ion.19b,36 The magnetic Conclusions
susceptibility of 4 above 240 K follows the Curie-Weiss Through a preheating and cooling-down crystalliza-
law because of the presence of thermally populated excited tion technique and in the presence of DMF, four new rare-
states. It should be pointed out that, because of the complex- earth carboxylate materials have been synthesized. This
synthetic approach not only reduces the possibility of
(32) Gamelin, D. R.; Wermuth, M.; Güdel, H. U. J. Lumin. 1999, 83-84,
405.
involvement of coordination water molecules in the com-
(33) Karbowiak, M.; Edelstein, N. M.; Droz̆dz̆yński, J. J. Lumin. 2003, pounds but also improves the solubility of aromatic car-
104, 197. boxylic acids and therefore the formation of single crystals
(34) Andruh, M.; Bakalbasis, E.; Kahn, O.; Trombe, J. C.; Porcher, P. Inorg.
Chem. 1993, 32, 1616. suitable for structural analysis. The solid-state luminescent
(35) Kahn, M. L.; Sutter, J.-P.; Golhen, S.; Guionneau, P.; Ouahab, L.; spectra demonstrate that compounds 1 and 4 are red
Kahn, O.; Chasseau, D. J. Am. Chem. Soc. 2000, 122, 3413.
(36) Wu, C.-D.; Lu, C.-Z.; Yang, W.-B.; Lu, S.-F.; Zhuang, H.-H.; Huang, luminescent materials potentially useful for optical devices
J.-S. Eur. J. Inorg. Chem. 2002, 797. and compound 2 is a good candidate for a near-IR-emitting
2864 Inorganic Chemistry, Vol. 45, No. 7, 2006
2D and 3D Rare-Earth Coordination Polymers

application. Furthermore, compound 2 exhibits interesting Acknowledgment. This work was supported by the
up-conversion properties with UV and intense blue up- National Natural Science Foundation of China and the
conversion emissions upon 580-nm excitation. The magnetic Education Ministry of China.
properties of compounds 1, 2, and 4 were also studied by Supporting Information Available: Four X-ray crystallo-
measuring their magnetic susceptibility over the tempera- graphic files (CIF), selected bond distances and angles, FTIR
ture range of 4-300 K. It is anticipated that other new spectra, and simulated and experimental powder XRD patterns for
lanthanide carboxylate compounds with interesting structures compounds 1-4 and a UV-vis spectrum for the NDC ligand. This
as well as physical properties may also be synthesized material is available free of charge via the Internet at http://
pubs.acs.org.
through the preheating and cooling-down crystallization
approach. IC051557O

Inorganic Chemistry, Vol. 45, No. 7, 2006 2865