An unusual 2-fold interpenetrated 3D PtS framework containing circular and rhombic tubular building blocks and hydrogen-bonded -O-metal-O-chain

Article abstract of DOI:10.1016/j.inoche.2009.05.015

Circular and rhombic tubular building blocks interweave mutually into a novel 2-fold interpenetrated 3D PtS framework [Zn(ADB)(H₂O)]_n (1) (H₂ADB = azobenzen-4,4′-dicarboxylic acid), with hydrogen-bonded-O-metal-O-chain. In

Full text of DOI:10.1016/j.inoche.2009.05.015

Inorganic Chemistry Communications 12 (2009) 657–659
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
An unusual 2-fold interpenetrated 3D PtS framework containing circular and
rhombic tubular building blocks and hydrogen-bonded –O–metal–O–chain
b
b
b
a
c,
*
Feng Fu a,b, Dong-Sheng Li a,b, , Xiao-Gang Yang , Cui-Qiao Zhang , Ya-Pan Wu , Jun Zhao , En-Bo Wang
*
a College of Mechanical & Material Engineering, Functional Materials Research Institute, China Three Gorges University, Yichang 443002, China
b School of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan0an University, Yan0an 716000, China
c Department of Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Northeast Normal University, Changchun 130024, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Circular and rhombic tubular building blocks interweave mutually into a novel 2-fold interpenetrated 3D
PtS framework [Zn(ADB)(H2O)]n (1) (H2ADB = azobenzen-4,40-dicarboxylic acid), with hydrogen-bonded–
O–metal–O–chain. In additional, solid-state properties such as photoluminescence and thermal stability
of the complex 1 have also been studied.
Received 6 January 2009
Accepted 19 May 2009
Available online 27 May 2009
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Metal-organic frameworks
Building block
Interpenetration
Luminescent property
Due to the intriguing structural topologies and potential appli-
cations as functional solid materials, the investigation of metal-or-
ganic frameworks (MOFs), built from metal clusters and
multifunctional carboxylates, have been a field of rapid growth
[1–5]. Among them, zinc coordination polymers have attracted
much attention owing to their thermal stability and photolumines-
cent properties [6,7]. In where, the multinuclear zinc clusters,
which act as building blocks, can be used to build up extended
frameworks [8–10], and to date, the zinc coordination polymers
with discrete multinuclear zinc clusters have been successfully iso-
lated [11–14]. However, the coordination polymers based on the
assembly of infinite multinuclear zinc clusters are scarce [12,15–
18]. It has been demonstrated that the presence of hydroxy or
oxo groups facilitates the formation of discrete clusters by
M–OH–M or M–O–M linkage [8,14], and this is also true for the
case of infinite building blocks. To best of our knowledge, there
are few examples in which the Zn–OH–Zn or Zn–(O–C–O)2–Zn con-
nectivity participates in the formation of one-dimensional (1D)
rod-shaped building blocks [15–18], and there is a recent report
of a 3D Zn coordination network with carboxylate-bridged Zn3
units and Zn chains [19], but such building blocks interweave
mutually into a 3D PtS framework contain hydrogen-bonded –O–
M–O– chain have not been reported so far.
In this context, along with our recent work on coordination
chemistry of a versatile organic ligand biphenylethene-4,40-dicar-
boxylic acid have presented distinct ZnII and CdII coordination
polymers, which exhibit intriguing 3D polycatenated array featur-
ing an uneven ‘‘density of catenation” and ninefold interlocked
homochiral helices [20,21], respectively, and thus triggered our
further activity on this topic, we chose a comparable multidentate
building block azobenzen-4,40-dicarboxylic acid (H2ADB) as bridg-
ing ligand, to prepare novel materials with intriguing architectures
and good physical properties, Fortunately, we have recently iso-
lated a new complex based on H2ADB, [Zn(ADB)(H2O)]n (1). The
structure of complex 1 exhibits unusual features: (i) the circular
and rhombic tubular building blocks interweave to form a 2-fold
interpenetrated network with PtS topology; (ii) the unique hydro-
gen-bonded –O–metal–O– chains enchase between the interpene-
trated frameworks.
Complex 1 was prepared by hydrothermal method in 66% yield
[22] and the structure was determined by X-ray single crystal dif-
fraction [23]. Structural analysis shows that the structure of 1 is a
3D neutral coordination polymer featuring two distinct tubular
structures constructed from zinc atom and ADB linkers, in which
the asymmetric unit contains one zinc atom, one ADB ligand, and
one coordinated water molecule. Each ligand possesses a 4-con-
nected geometry to connect the Zn atoms (Fig. S1) by bridging
bis-bidentate coordination modes, and each Zn atom adopts a dis-
torted trigonal bipyramid coordination mode to link one water
molecular and four separate ADB ligands (Fig. S2). The Zn–O bonds
* Corresponding authors. Address: College of Mechanical & Material Engineering,
Functional Materials Research Institute, China Three Gorges University, Yichang
443002, China. Tel./fax: +86 717 6397516 (D.-S. Li); Tel./fax: +86 431 85098787
(E.-B. Wang).
E-mail addresses: lidongsheng1@126.com (D.-S. Li), wangeb889@nenu.edu.cn
(E.-B. Wang).
1387-7003/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2009.05.015

658
F. Fu et al. / Inorganic Chemistry Communications 12 (2009) 657–659
fall in the range of 1.962(5)–2.218(6) Å (Table S1). The shortest
Znꢀ ꢀ ꢀZn separation connected by the same carboxylate group is
4.372 Å, while the shortest one connected by the space unit of
the ADB ligand is 15.950 Å.
is in accord with the fact that tetrahedral, trigonal, and octahedral
metal templates have a high tendency to form interpenetrated or
self-inclusion compounds, if the cavity generated in this way is
more than 50% of the crystal by volume [32].
The most striking feature of complex 1 is the alternately ar-
ranged two distinct tubular structures (Fig. 1). In order to interpret
the whole network clearly, the structure of 1 could be described as
two kinds of building blocks, circular (block A) and rhombic (block
B) tubes. Firstly, the bridge of the carboxyl pattern of the ADB li-
gands leads to form infinite Zn–(O–C–O)2–Zn rod-shaped building
blocks running along the b axes, namely circular tube (block A).
Secondly, the rods of block A are linked by the ADB arms (as the
spacer), which connect each rod to four neighboring rods along
the c-axis, giving rise to rhombic tube building blocks (block B).
Notably, such tubular building blocks are not isolated but inter-
weaved with each other across Zn atom, and decorated with coor-
dinated water molecules alternately at two sides. Moreover, when
viewed along the c-axis, it can be found that blocks A and B are
alternately arranged, leading to a complicated 3D network.
Not surprisingly, from the topological point of view, when each
ligand acts as a square-planar node, and each central atom can be
looked as a 4-connecting tetrahedral/square-planar node, the
whole structure can be represented to a PtS/lvt net [24,25], in
our work, each ligand and five-coordinated Zn atom can be de-
scribed as a square-planar and tetrahedral node, respectively, thus
interweaving of tubular building blocks leads to a 3D network with
a PtS topology, as displayed in Fig. 2a. Furthermore, owing to no
bulky solvent molecules occupied in the crystal, two such nets
interpenetrate with catenation of just the large rhombic channels
of 25.55 ꢁ 10.90 Å along the c-axis (Figs. 2b and S3), and there
are some examples of the interpenetrated PtS nets [24,26–31]. This
Another remarkable character of the complex 1 is the formation
of hydrogen-bonded –O–metal–O– chains that is made up of (–O–
Hꢀ ꢀ ꢀO–Zn–Oꢀ ꢀ ꢀH–O–)n repeat units and Zn–O bridging group
(Fig. S4). In 1, the arrangement of the 2-fold interpenetration pro-
vides an opportunity to form the hydrogen-bonded chains, which,
in turn, play an important role in the stability of interpenetrated
structure. The coordinated water molecule (O3) of one framework
acts as the hydrogen-bond donor and the carboxylic oxygen (O1) of
the other framework as hydrogen-bond acceptor (O3–Hꢀ ꢀ ꢀO1
2.687 Å 164.32°), additionally, the coordinated water molecules
(H–O3–H: 107.97°), which decorated alternately at two sides of
circular tube, play a orienting action at an angle, leading to the for-
mation of chains. More wonderfully, Zn–O3 group represent as a
bridge by linking the adjacent chains, giving rise to the arrange-
ment of hydrogen-bonded chains. Recently, a rare –metal–O–me-
tal– helix has been reported [33], in which, the arrangement of
the triple-helical chains provided an opportunity to form the sin-
gle-helical chain. As far as we know, 1 represents the first example
of metal-organic framework containing hydrogen-bonded –O–me-
tal–O– chain.
To examine the thermal stability of the whole frameworks,
thermal gravimetric analysis (TGA) and X-ray powder diffraction
(XRPD) measurements were carried out (Figs. S5 and S6). For com-
plex 1, the TGA trace exhibits two weight losses: one (5.66%) from
145 to 190 °C is attributed to the loss of two coordinated water
molecules (calcd 5.12%); the other from 400 to 600 °C corresponds
to the removal of the ADB ligand. The final product is assumed to
Fig. 1. (a) Infinite Zn–O–C–O rod-shaped building block running along the b-axis. (b) Schematic view of infinite rod-shaped building block (block A). (c) Left: the perspective
view of block A are linked by the ADB arms (block B), right: schematic view of block B. (d) Left: the framework of 1 viewed along the c-axis (coordinated water molecules are
omitted for clarity), right: schematic view of the two types of tubes arranged alternately along the c-axis.

F. Fu et al. / Inorganic Chemistry Communications 12 (2009) 657–659
659
Fig. 2. (a) 3D coordination framework of 1 with PtS topology (color codes: blue for 4-connected tetrahedral nodes, yellow for 4-connected square-planar nodes); (b) Space-
filling view of the 2-fold interpenetration in 1. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
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be ZnO (found weight 23.02), which is supported by the expected
(PXRD) patterns (Fig. S6, beyond 400 °C, the diffraction peaks of
ZnO appear). Notably, the XRPD measurement is in accordance
with the TGA analyses. In addition, photoluminescence property
of powder samples of 1 has also been examined at room tempera-
ture (Fig. S7). Up on the excitation at 300 nm, complex 1 exhibits
an intense emission at 413 nm, while the free H2ADB ligand dis-
plays weak luminescence at 422 nm. The luminescent behavior
of 1 is such that its high-dimensional condensed polymeric struc-
ture leads to significant enhancement of fluorescence intensity
compared to the free ligand. The blue-shift (about 9 nm) of this
emission bands with respect to the free H2ADB ligand is probably
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*
*
due to the (
p
–p) transitions changing into the (
p
–n) transitions
after forming the coordination polymer. The enhanced lumines-
cence efficiency is therefore attributed to ADB coordinated to ZnII
ions resulting in a decrease in the nonradiative decay of intraligand
excited states [24,34,35].
In summary, we have prepared and characterized an unusual 2-
fold interpenetration 3D PtS framework assembled from circular
and rhombic tubular building blocks. Meanwhile, the first hydro-
gen-bonded –O–metal–O– chains were formed between the inter-
penetrated frameworks. In addition, complex 1 shows strong
fluorescent emission. Further studies for the construction of novel
coordination polymers with unusual topologies and interesting
physical properties, by reacting long spacer ligand and different
metal ions, are progress.
6 (2006)
[22] Synthesis of [Zn(ADB)(H2O)]n (1): A mixture of Zn(NO3)2ꢀ6H2O (0.5 mmol,
0.149 g), H2ADB (0.5 mmol, 0.123 g), triethylamine (0.15 mL), and deionized
water (9 mL) was stirred for 20 min in air, then transferred and sealed in a
23 mL Parr Teflon-lined stainless steel vessel, which was heated at 120 °C for
6 days, and then cooled to room temperature. Orange yellow crystals were
obtained (yield 66%). Elemental analysis calc. for C14H10N2O5Zn (%): C, 47.82;
H, 2.87; N, 7.97. Found: C, 47.78; H, 2.89; N, 7.94. Selected IR(KBr) spectra for
1:
m
(cmꢂ1) 3152 (s), 1598 (m), 1542 (m), 1419 (m), 1397 (m), 1073(w),
1010(w),772(m),724 (w), 679 (w), 642(w).
[23] Crystal diffraction intensities for 1 were collected at 293(2) K with a Siemens
Acknowledgements
SMART system equipped with
a CCD detector with Mo Ka radiation at
0.71073 Å. Absorption corrections were applied using SADABS program. The
structure was solved with direct methods and refined with the full-matrix
least-squares technique based on F2 using the SHELXTL program package.
Anisotropic thermal parameters were applied to all non-hydrogen atoms. The
hydrogen atoms were placed in constrained positions with isotropic
temperature factors. Crystal data: formula C14H10N2O5Zn, M = 351.62,
Monoclinic, space group P2/c, with a = 14.6000(2) Å, b = 6.4230(15) Å,
This work was financially supported by the National Natural
Science Foundation of China (No. 20773104), the Program for
New Century Excellent Talents in University (NCET-06-0891), the
Key Project of Key Laboratory of Shaanxi Province (08JZ81), the
Important Project of Hubei Provincial Education Office
(Z20091301), and the Natural Science Foundation of Hubei/Sha-
anxi Provinces of China (2008CBD030/SJ08B11).
c = 7.3600(16) Å,
a
= 90ꢀ, b = 91.040(2ꢀ),
c
l
= 90ꢀ, V = 690.08(24) Å3, T = 293(2) K,
= 1.805 mmꢂ1, the final R1 = 0.0730,
Z = 2, F(0 0 0) = 356, Dc = 1.692 g cmꢂ3
,
wR2 = 0.2253 (all data), and GOF = 1.019.
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Appendix A. Supplementary material
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Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.inoche.2009.05.015.
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