Two novel isostructural Ln (III) 3D frameworks supported by 3,6-dibromobenzene-1,2,4,5-tetracarboxylic acid and in situ generated oxalate: Syntheses, characterization and photoluminescent property

Article abstract of DOI:10.1016/j.inoche.2012.09.023

Two isostructural lanthanide complexes, [Ln (dbtec)_0.5(ox) _0.5·3H₂O]_n, [Ln = Dy (1), Yb (2)] (H₄dbtec = 3,6-dibromobenzene-1,2,4,5-tetracarboxylic acid; H ₂ox = oxalic acid), have been synt

Full text of DOI:10.1016/j.inoche.2012.09.023

Inorganic Chemistry Communications 26 (2012) 51–55
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Two novel isostructural Ln (III) 3D frameworks supported by
3,6-dibromobenzene-1,2,4,5-tetracarboxylic acid and in situ generated oxalate:
Syntheses, characterization and photoluminescent property
⁎
Liangliang Zhang, Jie Guo, Qingguo Meng, Haiduo Pang, Zhen Chen, Daofeng Sun
Key Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, Shandong 250100, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Two isostructural lanthanide complexes, [Ln (dbtec)0.5(ox)0.5·3H2O]n, [Ln=Dy (1), Yb (2)] (H4dbtec=3,6-
dibromobenzene-1,2,4,5-tetracarboxylic acid; H2ox=oxalic acid), have been synthesized under the hydro-
thermal method and characterized by single-crystal X-ray diffraction, X-ray powder diffraction (PXRD),
thermogravimetric analysis (TGA) and elemental analysis (EA) and IR spectra. Complex 1 and 2 present a
2-nodal (4,6)-connected 3D fsc network. The 13C NMR of H4dbtec indicates ox in 1 and 2 is generated by
the in situ decomposition of H4dbtec. Additionally, the photoluminescent properties of 1 and 2 are also
discussed.
Received 3 September 2012
Accepted 21 September 2012
Available online 27 September 2012
Keywords:
Crystal structure
Lanthanide
Luminescence
fsc network
© 2012 Elsevier B.V. All rights reserved.
In situ reaction
The rational design and synthesis of functional metal-organic frame-
works (MOFs) is a more and more fascinating field due to their interest-
ing topologies and potential applications in gas adsorption, nonlinear
optics, magnetism, luminescence, molecular recognition, etc. [1–3]. Or-
ganic carboxylate ligand is currently a good candidate to construct
MOFs, because it can not only provide a number of coordination sites
to coordinate to metal ions through coordinative bonds, but also act as
hydrogen-bonding acceptors or donors to further extend low-
dimensional frameworks to high-dimensional architectures through
hydrogen-bonding interactions [4]. Meanwhile, the utilization of poly-
nuclear metal clusters as secondary building units (SBUs) to construct
high-connected frameworks has been proved to be an effective method
[5]. In addition, lanthanide elements were selected to constructed net-
work, owing to their high 8–12 coordination numbers and flexible
Ln-O bond lengths, which allow forming new topological and interest-
ing fluorescent properties [6]. At the same time, in hydro- or
solvothermal reactions, some unexpected in situ ligand reactions may
occur involving organic ligand in the presence of metal ion, which
makes accurately predicting final structures more difficult [7]. In fact,
oxalate in situ generation under several conditions is quite widespread
and investigated and has been used to generate coordination com-
pounds and MOFs with a variety of transition metal and lanthanide
ions. The mechanism of in situ formation of oxalic acid is also being
studied. Considering these in mind, we constructed two isostructural
lanthanide complexes, [Ln (dbtec)0.5(ox)0.5·3H2O]n, [Ln=Dy (1),
Yb (2)] [H4dbtec=3,6-dibromobenzene-1,2,4,5-tetracarboxylic acid
(Scheme 1); H2ox=oxalic acid], which were constructed from
H4dbtec and in situ generated ox ligand.
Single-crystal X-ray analysis of 1 and 2 indicates that they are
isostructural, so the structure of 1 is described representatively here in
detail. Complex 1 was synthesized by the reaction of Dy (NO3)3·3H2O
and H4dbtec through the conventional hydrothermal method [8] in a
pressure-resistant glass tube. X-ray single-crystal diffraction reveals
[9] that compound 1 is a three-dimensional framework and crystallizes
in triclinic P-1 space group. The asymmetric unit contains one crystallo-
graphic independent Dy (III) ion, half dbtec ligand, half ox ligand, and
three coordinated water molecules. As shown in Fig. 1, Dy1 is eight co-
ordinated by three carboxylate oxygen atoms (O2ii, O3i, O4) from three
different dbtec ligands, three oxygen atoms (O1W, O2W, O3W) from
three coordinated water molecules and two oxygen atoms (O5, O6)
from one ox ligand molecular, exhibiting a slightly distorted square
antiprism configuration. The bond distances of Dy-Odbtec, Dy-Owater
and Dy-Oox are in the ranges of 2.286 (7)–2.373 (6) Å, 2.374 (7)–
2.442 (7) Å, and 2.374 (6)–2.451 (6) Å, respectively (Table S1). The bro-
mide atoms and benzene ring in dbtec ligand are essentially planar,
with mean deviations of 0.034 (1) Å, from the least-squares plane de-
fined by C1/C2/C3/C4/Br atoms. The dihedral angles formed by carbox-
ylate group (O1/O2ii/C1, O3i/O4/C5) and central benzene ring range
from 65.536 (19) ° to 78.251 (26) °. All of bond lengths and angles are
comparable to those reported dysprosium complexes [10] (symmetry
codes: (i) 1−x, 1−y, −z; (ii) 2−x, 1−y, 1−z).
For the coordination mode of ox ligand, it is in a μ2-bridging mode to
link two Dy ions (Fig. 2a). As for btec ligand, four carboxylate groups of
each btec adopts two kinds of coordination modes: one pair of the
inversion-related carboxylate groups of one btec exhibit a μ1-η1-η0
⁎
Corresponding author. Fax: +86 531 88364218.
E-mail address: dfsun@sdu.edu.cn (D. Sun).
1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.inoche.2012.09.023

52
L. Zhang et al. / Inorganic Chemistry Communications 26 (2012) 51–55
formation has largely been a serendipitous process. Because of C–C
bond formation or cleavage, oxidation, and decarboxylation, among
many others, the organic starting material may undergo a variety of re-
actions, so the products of these reactions are not always intuitive [16].
Recently, a research paper “Exploring the mechanism of in situ forma-
tion of oxalic acid for producing mixed fumarato-oxalato lanthanide
(Eu, Tb and Gd) frameworks” has been published. Based on the mecha-
nisms mentioned in that paper together with the 13C NMR of H4dbtec,
we concluded that ox ligand in 1 and 2 was formed by in situ hydrolysis
of H4dbtec ligand mediated by Ln3+ followed by oxidation and decar-
boxylation steps, which paved the way for understanding the dual role
of Ln3+ ions and the nature of the oxidant in forming the frameworks
[17].
The powder X-ray diffraction (PXRD) pattern of 1 and 2 was also
investigated. The simulated and experimental PXRD patterns of 1
and 2 are shown in Fig. S1 indicating the phase purity of the products.
The most peak positions of simulated and experimental patterns are
in good agreement with each other; the differences in intensity may
be due to the preferred orientation of the powder samples [18].
In 1 and 2, the observed broad peak at 3500 cm−1 in the FT-IR
spectrum (Fig. S2) is attributed to the O–H stretching vibration of
the coordinated water molecules, and the sharp bands in the ranges
of 1690–1605 and 1440–1330 cm−1 are attributed to asymmetric
and symmetric stretching vibrations of carboxylic group, respectively
[19].
To better understand the coordinated water and the thermal stabil-
ity of 1 and 2, thermal gravimetric analysis (TGA) was performed.
Thermogravimetric analysis of 1 and 2 was carried out under a
nitrogen-flow atmosphere with a heating rate of 10 °C min−1 in the
temperature region of 30–800 °C. Because of the isostructure of 1 and
2, the two compounds exhibited similar thermal stability as shown in
Fig. S3, and the TG curve displays mainly two steps of weight loss pro-
cesses. TGA indicates that 1 and 2 are stable up to ca. 430 °C. A loss
weight of 12.01% observed between 150 and 300 °C for 1 and 11.51%
observed for 2 corresponds to the full release of lattice water molecules
(calcd: 11.65% for 1 and 11.39% for 2). The second process began from
ca. 410 °C, corresponding to the decomposition of dbtec organic ligands
as well as ox ligand, which is nearly in agreement with the single-crystal
analysis.
Scheme 1. The synthesis route of H4dbtec.
mode, and the other couple inversion-related carboxylate groups dis-
play a μ2-η1-η1 bridging mode, and so the btec ligand exhibits
μ6-η1-η0-η1-η1-η1−η1-η1-η0 bridging fashion linking six Dy ions
(Fig. 2b). So dbtec ligand were linked by four dinuclear Dy (III) SBUs
to form a 2D layer and then the neighboring layer was further
connected by ox ligand to form the whole 3D crystal structure of 1
(Fig. 2c). The intramolecular hydrogen bonds between uncoordinated
O atom of carboxylate group and coordinated water molecules stabi-
lized the final structure. To better understand the complicated structure
of compound 1, the topological analysis of complex 1 has been
performed by the TOPOS software [11]. Each dbtec linking four dinucle-
ar Dy (III) SBUs unit is defined as a 4-connected node (Fig. 3a), and each
dinuclear Dy (III) SBUs was linked by two adjacent dinuclear Dy (III)
SBUs and four dbtec ligand, forming a 6-connected node (Fig. 3b). The
whole three-dimensional net can be represented as
a 2-nodal
(4,6)-connected fsc network (Fig. 3c) with the Schlafli symbol of
{44.610.8}{44.62} identified and categorized by O'Keeffe et al., and struc-
tures containing fsc topological network have been reported rarely. As
far as we know, cor network is one of representation of (4,6)-connected
3D topology network with the style of corundum (Al2O3) [12], where
the geometries of 4- and 6-connected nodes are tetrahedron and octa-
hedron, respectively. But fsc topology features square 4-connected
node and octahedron 6-connected node, which makes an important
difference between each other. The first fsc topology was observed in
a coordination polymer, namely, [(CuI)7(DABCO)2.5 n
diazabicyclo[2.2.2]octane) [13]. Subsequently, the interpenetrated fsc
networks was also observed in [Cu (bbi)2(H2O) (β-Mo8O26 0.5] (bbi=
] (DABCO=1,4-
)
1,1′-(1,4-butanediyl)bis (imidazole)) [14]. Recently, an unusual
trinodal fsc network was discovered in a mixed-ligand coordination
polymer [15].
To prove the origination of ox ligand in 1 and 2, the 13C NMR (Fig. S4)
of H4dbtec was performed. By identification of 13C NMR of H4dbtec, we
ensured the purity of H4dbtec and no trace of H2ox exists in the starting
materials. So we deduced that H2ox originated from the in situ decom-
position of H4dbtec under the hydrothermal reaction. In situ ligand
The solid-state luminescent spectrum of 1, 2 and free ligand was
also investigated at room temperature. As shown in Fig. 4, the ligand
displays emission peak at 470 nm upon excitation at 302 nm, which
can be attributed to the π*—π transition of the p electrons of the aro-
matic rings. Compound 1 displays luminescent emission bands at 481,
572, 665 nm (λ ex=302 nm), respectively, which are attributed to
the characteristic emission for 4 9/2→6HJ (J=15/2, 13/2, 11/2) transi-
F
tion of the Dy (III) ion. The luminescence spectrum shows that the
blue emission intensity of the 4F9/2→6H15/2 transition is similar with
the yellow emission intensity of the 4F9/2→6H13/2 transition, and the
intensity of the 4F9/2→6H11/2 transition is much weaker. Compared
with the emission peak of the free ligand and compound 1, the
photoluminescence absence of ligand-based emission suggests effi-
cient energy transfer from the ligands to the lanthanide centers
upon excitation [20]. Compound 2 displays luminescent emission
bands at 447 nm (λ ex=302 nm). Compared with the emission
peak of the free ligand and compound 2, the luminescent behavior
of compound 2 is blue shift 23 nm which tentatively ascribed to
weaker interlumophore interactions that occur relative to the free li-
gand to different extents in their low-density crystal structures [21].
In summary, the syntheses and characterization of two new Ln
(III) compounds are described. Both 1 and 2 are (4,6)-connected 3D
fsc topology framework, in which ox ligand (in situ reaction generat-
ed) plays an important role in determining the 3D frameworks. The
luminescent behavior of compound 1 displays the characteristic
emission of Dy (III) ion, and compound 2 displays the emission
peak of the free ligand upon excitation at 302 nm.
Fig. 1. The coordination environment around Dy(III) ions in 1; all hydrogen atoms are
omitted for clarity (symmetry codes: (i) 1−x, 1−y, −z; (ii) 2−x, 1−y, 1−z).

L. Zhang et al. / Inorganic Chemistry Communications 26 (2012) 51–55
53
Fig. 2. (a) The coordination modes of ox ligand [symmetry codes: (i) 1−x, 2−y, −z.)]. (b) The coordination modes of and btec ligand in 1 [symmetry codes: (i) 1−x, 1−y, 1−z; (ii) 1−x,
1−y, −z; (iii) −1+x, y, z; (iv) x, y, 1+z; (v) 2−x, 1−y, 1−z)]. (c) Perspective view of the 3D structure of 1.
Fig. 3. (a) Each dbtec linking four dinuclear Dy (III) SBUs unit is defined as a 4-connected node. (b) Each dinuclear Dy (III) SBUs was linked by two adjacent dinuclear Dy (III) SBUs and four
dbtec ligand, forming a 6-connected node. (c) A schematic representation of (4,6)-connected fsc net of 1.

54
L. Zhang et al. / Inorganic Chemistry Communications 26 (2012) 51–55
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Acknowledgments
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This work was supported by the NSFC (grant no. 90922014), the
Shandong Natural Science Fund for Distinguished Young Scholars
(2010JQE27021), the NSF of Shandong Province (BS2009L007 and
Y2008B01), and Independent Innovation Foundation of Shandong
University (2010JQ011).
[8] [Dy (dbtec)0.5(C2O4)0.5 3H2O]n (1).
A mixture of Dy (NO3)3·3H2O (2 mg,
0.0058 mmol), H4dbtec (1 mg, 0.0024 mmol) and H2O (1 ml) were sealed in a
pressure-resistant glass tube and put into a programmed oven, slowly heated to
120 °C from room temperature in 600 min, kept at 120 °C for 3000 min, After slowly
cooled to 30 °C in 800 minutes colorless block crystals of 1 were separated in 52.1%
yield based on ligand. Elemental analysis: Anal. Calc. for C6H5BrDyO9: C 15.52, H
1.09%. Found: C 15.40, H 1.00%. IR (KBr, cm−1): 3556 m, 1687 s, 1605 s, 1433 m,
1329 m, 1140 m, 893 w, 811 s, 757 w, 718 w 560 w, 502 w. [Yb (dbtec)0.5(C2O4)
Appendix A. Supplementary material
3H2O] n (2). A mixture of Yb (NO3)3·5H2O (2 mg, 0.0045 mmol), H4dbtec
0.5
CCDC 891409 and 891410 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/ retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB 21EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.
ac.uk. Supplementary data associated with this article can be found, in
the online version. Supplementary materials related to this article can
be found online at http://dx.doi.org/10.1016/j.inoche.2012.09.023.
(1 mg, 0.0024 mmol), H2O (1 ml) and 1drop dilute HCl (1 mol/l) were sealed in a
pressure-resistant glass tube and put into a programmed oven, slowly heated to
120 °C from room temperature in 600 min, kept at 120 °C for 3000 min, After slowly
cooled to 30 °C in 800 minutes colorless block crystals of 2 were separated in 47.6%
yield based on ligand. Elemental analysis: Anal. Calc. for C6H5BrYbO9: C 15.19, H
1.06%. Found: C 14.98, H 1.10%. IR (KBr, cm−1): 3560 m, 3456 m, 1690 s, 1610 s,
1436 s, 1330 s, 1141 m, 815 m, 560 m.
[9] Crystal data for 1: triclinic P-1 space group, a=6.265(4) Å, b=9.327(6) Å,
c=9.926(6) Å, α=108.325(8) ° β =107.268(9) ° γ=90.577(9) ° V=522.3(6)
Å3, Z=2, ρ=2.915 g/cm3, F (000)=418, μ=11.012 mm−1, 2865 reflection mea-
sured, 2168 unique (Rint=0.000), final R1=0.0433, wR2=0.1183 for all data; 2:
triclinic P-1 space group, a=6.1925(13) Å, b=9.2427(19) Å, c=9.845(2) Å,
α=108.222(3) ° β =107.484(3) ° γ=90.664(3) ° V=507.02(18) Å3, Z=2,
ρ=3.092 g/cm3, F (000)=432, μ=13.200 mm−1, 2450 reflection measured,
1739 unique (Rint=0.000), final R1=0.0405, wR2=0.1328 for all data; data col-
lection of 1 and 2 were performed with MoKα radiation (Kα=0.71073 Å) on a
Bruker APEX-II diffractometer. The structures were solved by direct methods and
all non-hydrogen atoms were subjected to anisotropic refinement by full-matrix
least-squares on F2 using the SHELXTL program.
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