J Clust Sci (2010) 21:825–835

DOI 10.1007/s10876-010-0344-4

ORIGINAL PAPER

A New Rare-Earth Metal Coordination Polymer

Constructed from N-hetero Aromatic Multicarboxylate
Ligand

Hai-Jun Dong • Min Wang • Shu-Wei Huang •

Yan-Ling Wu • Hao-Hong Li • Zhi-Rong Chen

Received: 17 May 2010 / Published online: 1 September 2010

Ó Springer Science+Business Media, LLC 2010

Abstract The hydrothermal reaction of Gd(NO3)36H2O with 2,20 -bipyridyl-4,40 -

dicarboxylic acid(H2BPDC) ligand results in the formation of a new Gd(III) polymer:
{[Gd2(BPDC)3(H2O)3]H2O}n..(1). The central gadolinium ion is coordinated by eight
oxygen atoms to give a dicapped triangular prism geometry. Based on the versatile
coordination modes of BPDC2- ligand, together with hydrogen bonds and pp stacking
interactions, a 3-D network is presented. DFT calculation was executed to probe the
electronic structure of 1.

Keywords Aromatic carboxylate  Gd complex  Co-ordination polymer

Introduction

Metal–organic co-ordination polymers [1, 2], especially rare earth metal-containing

co-ordination polymers have attracted continuous attention due to their potential
applications as function materials such as catalysis, non-linear optics, and porous
materials, which stem from their unique 5d and 4f electron configurations [3–6]. So
far, the coordinated chemistry of the rare earth metal is virtually underdeveloped
because of some intrinsic characteristics such as the high and variable coordination
numbers as well as the small energy difference among various coordination
geometries [3]. Aromatic multicarboxylates are good building blocks for the
construction of metal–organic coordination polymers due to their versatile
coordinated modes of carboxyl groups, and a series of interesting lanthanide
polymers have been obtained by employing benzoic multicarboxylate ligands [7–9].

H.-J. Dong  M. Wang  S.-W. Huang  Y.-L. Wu  H.-H. Li (&)  Z.-R. Chen (&)
College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350108, Fujian, China
e-mail: [email protected]
Z.-R. Chen
e-mail: [email protected]

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826 H.-J. Dong et al.

2,20 -bipyridyl-4,40 -dicarboxylic acid (H2BPDC) is another kind of aromatic

multicarboxylates, whose two pyridine rings are linked by r-bond. Due to the
good flexibility of r-bond, two pyridine rings can rotate in some extend, leading to
versatile conformations and coordination modes. So dimension extention will be
achieved due to the better flexibility of this ligand than that of benzoic
multicarboxylate ligands. It is a good building block for the construction of rare
metal polymers through full or partial deprotonation of its carboxylic groups
[10–13]. But up to now, the rare earth metal coordination polymers constructed
from H2BPDC are still rare [14–17]. In this work, through hydrothermal reaction of
2,20 -bipyridyl-4,40 -dicarboxylic acid with Gd(III), we have obtained a new open
framework structure {[Gd2(BPDC)3(H2O)3]H2O}n. (1).

Experimental

General Remarks

All chemicals were analytically pure and used without any purificaiton. Elemental
analysis was performed on a Vario MICRO instrument. The infrared spectra of
single crystals was recorded with a Perkin–Elmer Spectrum-2000 FTIR spectro-
photometer (4000–400 cm-1) on powdered sample spread on KBr plate. Optical
diffuse reflectance spectrum was measured on a PE Lambda 35 UV–vis
spectrophotometer equipped with an integrating sphere at 293 K, and the BaSO4
plate was used as the reference. Fluorescence spectrum was carried out on a
PW2424 spectrometer. X-ray powder diffraction (XRD) was performed on a Rigaku
X-ray MiniFlexII diffractometer.

Preparation of Complex

A mixture of Gd(NO3)36H2O (0.25 g, 0. 5 mmol), 2,20 -bipyridyl-4,40 -dicarboxylic

acid (0.12 g, 0.5 mmol) and H2O (10.0 mL) in a mol ratio of ca. 1:1:1111 was
sealed in a 25 mL stainless-steel reactor with Teflon liner and directly heated to
160 °C and kept reacting for 3 days, then cooled to room temperature during 24 h.
Light gray prism-like crystals of complexe were obtained in 24% yield. Anal. Calcd.
(%) for C36H24Gd2N6O16: C, 38.91; H, 2.17; N, 7.56. Found (%): C, 39.13; H, 2.22;
N, 7.66. IR (KBr, cm-1): 3320(s), 3067(s), 1647(w),1599(w), 1579(s), 1545(s),
1472(m), 1463(m), 1445(s), 1272(w), 1244(w), 1155(w), 1095(w), 1060(w), 999(s),
903(w), 879(w), 773(s), 739(m), 712(s), 678(s),562(m), 422(m) (Tables 1, 2).

Crystallography

A gray prism-like crystal with dimensions of 0.30 9 0.25 9 0.20 mm was mounted
on a glass fiber. The data collection was performed at 293(2) K on a SIEMENTS
SMART CCD diffractometer with graphite-monochromated MoKa (k = 0.71073
Å) radiation by using an x/2h scan in the range of 3.23 B h B27.51°. Out of the
total reflections of 14723, 8097 were independent with Rint = 0.0350, of which

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Table 1 Selected bond lengths (Å) and bond angles (°)

Atoms Distances Atoms Distances

Gd(1)–O(14) 2.235(3) Gd(1)–O(16) 2.298(3)

Gd(1)–O(12) 2.306(3) Gd(1)–O(11) 2.318(3)
Gd(1)–O(8) 2.412(3) Gd(1)–O(13) 2.424(3)
Gd(1)–O(15) 2.425(3) Gd(1)–O(4) 2.755(3)
Gd(2)–O(9)#1 2.281(3) Gd(2)–O(5) 2.302(3)
Gd(2)–O(4) 2.322(3) Gd(2)–O(3) 2.328(4)
Gd(2)–O(7) 2.351(3) Gd(2)–O(6) 2.406(3)
Gd(2)–O(2) 2.421(3) Gd(2)–O(8) 2.534(3)
Gd(1)–Gd(2) 4.0461(17)

Atoms Angles Atoms Angles

O(14)–Gd(1)–O(16) 87.02(12) O(14)–Gd(1)–O(12) 96.03(12)

O(16)–Gd(1)–O(12) 148.04(11) O(14)–Gd(1)–O(11) 98.02(11)
O(16)–Gd(1)–O(11) 139.70(11) O(12)–Gd(1)–O(11) 71.51(12)
O(14)–Gd(1)–O(8) 160.58(11) O(16)–Gd(1)–O(8) 81.29(11)
O(12)–Gd(1)–O(8) 102.11(12) O(11)–Gd(1)–O(8) 81.42(11)
O(14)–Gd(1)–O(13) 77.82(12) O(16)–Gd(1)–O(13) 71.21(11)
O(12)–Gd(1)–O(13) 140.56(11) O(11)–Gd(1)–O(13) 70.91(11)
O(8)–Gd(1)–O(13) 83.73(11) O(14)–Gd(1)–O(15) 74.94(11)
O(16)–Gd(1)–O(15) 75.15(11) O(12)–Gd(1)–O(15) 75.00(12)
O(11)–Gd(1)–O(15) 144.82(12) O(8)–Gd(1)–O(15) 116.36(11)
O(13)–Gd(1)–O(15) 137.33(11) O(14)–Gd(1)–O(4) 124.01(10)
O(16)–Gd(1)–O(4) 76.13(11) O(12)–Gd(1)–O(4) 75.88(12)
O(11)–Gd(1)–O(4) 128.79(10) O(8)–Gd(1)–O(4) 68.06(10)
O(13)–Gd(1)–O(4) 139.52(10) O(15)–Gd(1)–O(4) 49.25(10)
O(9)#1–Gd(2)–O(4) 85.04(12) O(5)–Gd(2)–O(4) 74.01(13)
O(9)#1–Gd(2)–O(3) 98.83(17) O(5)–Gd(2)–O(3) 143.15(15)
O(4)–Gd(2)–O(3) 69.49(15) O(9)#1–Gd(2)–O(7) 83.33(12)
O(5)–Gd(2)–O(7) 69.32(12) O(4)–Gd(2)–O(7) 142.61(12)
O(3)–Gd(2)–O(7) 147.52(14) O(9)#1–Gd(2)–O(6) 152.68(12)
O(5)–Gd(2)–O(6) 116.05(13) O(4)–Gd(2)–O(6) 118.17(12)
O(3)–Gd(2)–O(6) 78.26(17) O(7)–Gd(2)–O(6) 85.19(12)
O(9)#1–Gd(2)–O(2) 77.63(13) O(5)–Gd(2)–O(2) 140.49(12)
O(4)–Gd(2)–O(2) 136.62(13) O(3)–Gd(2)–O(2) 74.29(15)
O(7)–Gd(2)–O(2) 74.59(13) O(6)–Gd(2)–O(2) 75.44(12)
O(9)#1–Gd(2)–O(8) 155.04(11) O(5)–Gd(2)–O(8) 79.53(11)
O(4)–Gd(2)–O(8) 73.34(11) O(3)–Gd(2)–O(8) 85.37(15)
O(7)–Gd(2)–O(8) 106.26(11) O(2)–Gd(2)–O(8) 126.85(11)

Symmetry codes: #1 -x ? 1, -y ? 1, -z

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828 H.-J. Dong et al.

Table 2 Hydrogen bond lengths (Å) and bond angles (°)

D–H d(D–H) d(HA) \DHA d(DA) A

O(3)–H(3A) 0.868 1.814 173.32 2.678 O(1)

O(2)–H(2A) 0.955 2.080 158.49 2.989 N(3) [–x ? 2, -y ? 2, -z]
O(2)–H(2B) 0.990 1.863 166.69 2.836 O(7) [-x ? 1, -y ? 1, -z]
O(13)–H(13A) 1.041 1.735 172.13 2.769 N(2) [x-1, y, z]
O(13)–H(13B) 1.034 2.173 148.64 3.103 N(1) [x, y ? 1, z]
O(13)–H(13B) 1.034 2.651 111.84 3.183 O(14) [–x ? 2, -y ? 2, -z ? 1]
O(3)–H(3B) 0.976 1.709 169.83 2.675 O(10)

7939 were considered to be observed (I C 2r(I)) and used in the succeeding

refinement. The intensity data were corrected with empirical absorption. The structure
was solved by direct method in SHELXS-97 program [18]. All of the non-hydrogen
atoms and some of the hydrogen atoms were located by successive difference Fourier
synthesis, and the anisotropic thermal parameters for non-hydrogen atoms were
refined by full-matrix least-squares techniques on F2 calculation for 561 parameters.
The final cycle of refinement gave rise to R1 = 0.0362, wR2 = 0.0960, w =
1/[r2(FO)2 ? (0.0553P)2 ? 3.0680 P], where P = (F2O)max ? 2F2c )/3, S = 1.145,
(D/r)max = 0.000, (Dq)max = 1.392, (Dq)min = -2.172 e/Å3.

Results and Discussion

Description of Crystal Structure

Single crystal X-ray analysis reveals that {[Gd2(BPDC)3(H2O)3]H2O}n.(1) is a

three-dimensional framework constructed from versatile coordination modes of
carboxyl groups, hydrogen bond interactions and pp stacking interactions. The
structure of [Gd2(BPDC)3(H2O)3]n. framewrok can be discussed in terms of Gd2O14
cluster. In the Gd2O14 cluster, Gd(1) is in eight-coordinated dicapped triangular
prism environment, where six oxygen atoms are provided by carboxyl groups and
two oxygen atoms (O(2),O(3)) stem from water molecules. Gd(2) is also in eight-
coordinated dicapped triangular prism geometry, but its seven oxygen donors are
provided by carboxyl groups and only one oxygen donor (O(13)) is water. Gd(1)O8
dicapped triangular prism connects with Gd(2)O8 polyhedron via edge-sharing
mode (the edge is defined by O(4)–O(8)) to give a Gd2O14 cluster (Fig. 1). In other
words, Gd(1)O8 and Gd(2)O8 are linked by bis-monodentate bridge carboxyl (L2, as
defined in the following paragraphy). Gd(1)O8 dicapped triangular prism is highly
distorted with Gd–O distances ranging from 2.298(3) to 2.755(3)Å, but the
polyhedron of Gd(2) is much more normal with Gd–O distances being among
2.281(3)–2.534(3) Å. The Gd–Gd distance is 4.0461(17) Å, which is longer than the
sum of its atomic radius (3.6 Å), indicating the absence of direct metal–metal

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A New Rare-Earth Metal Coordination Polymer 829

Fig.1 Structure of Gd2O14 cluster revealing coordination mode of Gd centers

Fig. 2 Coordination modes of carboxyl groups in BPDC2- ligand

interactions. All the C–O bond lengths of deprotonated carboxyl groups are in
normal range (1.235(5) to 1.274(5) Å) [6].
The coordination mode of carboxyl groups is versatile in the title compound. The
observation of an absorption peak at 1635 cm-1 for –COO- in the IR spectrum
indicates the presence of deprotonated carboxylic groups in the complex, all the
–COOH is deprotonated with BPDC2- anion. To our interest, structural data show
there are three kinds of carboxylate ligands. The first is that the deprotonated
carboxylic group adopts a l4-bidentate chelating-bridging mode to connect four Gd
atoms (defined as L1, provide O(4), O(6), O(8), O(15) for Gd(1) and Gd(2) centers,
Fig. 2a). The second is that carboxylic group acts as l4-bridge with bis-monodentate
bridge mode to link four Gd atoms, in which each deprotonated carboxylic group
bridges two Gd atoms (defined as L2, provide O(7), O(9) for Gd(2) center, Fig. 2b).
The third is that the ligand acts as l2-bridge to link two Gd atoms, in which each
protonated carboxylic group coordinates to one Gd atom through one carbonyl

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830 H.-J. Dong et al.

Fig. 3 The 1-D chain structure linked by bis-monodenate bridge of L2

oxygen atoms (with monodentate bridge mode) (defined as L3, give O(10) for
coordinating to Cd(1) center, and O(12) is free, Fig. 2c). The series of IR peaks
ranging from 1647 to 1445 cm-1 (corresponding to vas and vs of –COO- groups)
also validate the rich coordinated modes of carboxyl groups. Two pyridine rings in
BPDC2- ligands are generally coplanar, except a small dihedral angle in L2
(11.75°) can be observed. As mentioned in the introduction, two pyridine rings are
linked by r-bond and exhibit good flexibility. As expect, a 180° rotation of two
pyridine rings can be found all BPDC ligands. As a result, versatile conformations
and coordination modes of carboxyl groups have achieved (Fig. 3).
Adjacent Gd2O14 clusters are linked by bis-monodentate carboxyl bridge of L2
(one of its carboxyl group) to give a 1-D chain along (111) direction (Fig. 3). The
1-D chain are extended to be a 2-D layer via monodentate carboxyl bridge of L3
(Fig. 4). And finally, adjacent layers are connected to be a 3-D network via
bidentate chelating-bridging and bis-monodentate carboxyl bridge of L1 and L2
(Fig. 5). In the layer-bridged ligands, a mediate pp stacking interactions
(barycenter distance: 3.818(13) Å between L1 and L2) can be observed between
pyridine rings. Finally, an isolated water molecule also stack in the crystal with the
total potential solvent accessible void volume of 79.6 Å3. Strong O–HO and
O–HN hydrogen bonds between this water and BPDC2- ligands can be detected
and contribute to the stabilization of the structure (Tabel 2).

UV–vis and Fluorescence Spectrum

The theoretical and experimental XRD patterns of 1 are generally the same, which
confirm its purity (Fig. 6). The UV–vis and fluorescence spectrum of 1 are given in
Fig. 7. In UV–vis adsorption spectrum (Fig. 7a), a strong peak at 311 nm could be

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A New Rare-Earth Metal Coordination Polymer 831

Fig. 4 The 2-D layer constructed from by monodenate bridge of L3

observed, around which a shoulder peak at 255 nm appears. Both of these

adsorptions could be attributed to the p–p* and n ? p* transfer of BPDC2- ligand.
The photoluminescence spectrum was measured in the solid state at room
temperature (Fig. 7b). On excitation at 380 nm, the intense photoluminescence
emissions for 1 are observed at 445, 459, and 531 nm. These emissions can be
explained as follows: p–p* transfer of BPDC2- ligand occur firstly, and then the
transfer from S0 to S1 singlet states can take place, afterwards it translates into
triplet state T1 exceeding the band gap, this transfer acts as a excited state to excite
the electron transition of trivalent gadolinium ion, and finally, these three
characteristic luminescence can be detected when the electrons transfer from
excited states to ground states [19, 20].

Electronic Structure

Electronic structure calculation was based on density function theory (DFT) [21,
22]. In the calculation, wave functions were explained in a plane wave basis set, and
the spin polarized version of the PW-91 GGA was employed for the exchange-
corelation functional with DMOL code [22]. The calculated band structure of 1 at
the Brillouin zone is shown in Fig. 8, in which the valence bands are flat and Fermi
energy level penetrates these bands, giving a conductor nature. The bands lying
deeply in valence band (-24.0 to -5.0 eV) are contributed from the Gd-5p,
O-2p and C, N-2s, 2p states. Importantly, the valence bands between -5.0 eV and
Fermi level (0.0 eV) are formed by Gd-4f as well as the mixture of small number of
O-2p and N-2p. The highest level at the valence bands are almost the contribution

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832 H.-J. Dong et al.

Fig. 5 The 3-D framewrok of 1

Theoretical simulation
Intensity (a.u.)

Experimental value

10 20 30 40 50
2theta (°)

Fig. 6 X-ray powder diffraction (XRD) patterns of 1

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A New Rare-Earth Metal Coordination Polymer 833

(a) 6 311nm
254nm
5

4
Intensity(a.u.)
3

-1
200 300 400 500 600 700 800
Wavelength(nm)

380nm
(b) 24000
445nm Em
325nm 459nm Ex
20000
531nm
intensity/a.u.

16000

12000

8000

4000

0
300 400 500 600 700
Wavelength(nm)

Fig. 7 UV–vis absorption spectrum (a) for solid-state fluorescence spectrum of 1(b)

from Gd-4f states. And the highest valence bands are composed by N-2p states
hybridized with small C-2p. Accordingly, UV adsorption peaks of 1 could be found
at 255 nm (4.86 eV) and 311 nm (3.98 eV), which is assigned as the charge
transfers of C-2 s/N-2p bonding orbitals to antibonding ones and in agreement with
the experimental attribution.

Conclusions

In conclusion, a new rare-earth metal coordination polymer {[Gd2(BPDC)3(H2O)3]

H2O}n. has been synthesized, which was constructed from N-hetero aromatic
multicarboxylate liagnd. The carboxyl group in BPDC2- ligand exhibits versatile
coordination modes, and hydrogen bond interactions and pp stacking interactions

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834 H.-J. Dong et al.

1
Energy/ev

-1

-2

-3

-4

-5
G F Q Z G

Fig. 8 Band structure of 1

in this polymer contributes to the formation of a 3-D network. DFT calculation was
executed to probe its electronic structure.

Supplementary Data

CCDC reference numbers: 747647. The supplementary crystallographic data for this
paper can bobtained from the Cambridge Crystallographic Data Center, 12 Unio
Road, Cambridge CB21EZ, UK; fax: (?44)1223-33-033; or emal:deposit@ccde.
cam.ac.uk.

Acknowledgment We acknowledge support of this research by National Natural Science Foundation of

China (NOS:20901017), specialized research fund for the doctoral program of higher education of
China(20093514120003) and Sci & Tech Promotion Foundation of Fuzhou University (2009-XQ-08).

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