New framework lodoargentates: M(en)3Ag2I4 (M = Zn, Ni) with tridymite topology

Article abstract of DOI:10.1021/ic7025158

Two novel framework compounds, Zn(en)₃Ag₂I ₄ (1) and Ni(en)₃Ag₂I₄ (2), have been synthesized by a self-assembly reaction. Both of them contain an unexpected framework, Ag₂I₄^2- with tridymite topolopy, and the discrete M(en)₃²⁺ cations are located in the channels. Their thermal properties and circular dichroism spectra were investigated.

Full text of DOI:10.1021/ic7025158

Inorg. Chem. 2008, 47, 3922-3924
New Framework Iodoargentates: M(en) Ag I (M ) Zn, Ni) with Tridymite
3
2 4
Topology
†
Yan-Si Jiang, Hua-Gang Yao, Shou-Hua Ji, Min Ji, and Yong-Lin An*
†
‡
†
,†
Departments of Chemistry and of Materials, Dalian UniVersity of Technology,
Dalian 116024, China
Received December 31, 2007
Two novel framework compounds, Zn(en) Ag
3
2
I
4
(1) and Ni(en) Ag
3
2
I
4
this reason, there is considerable interest in the synthesis of
microporous solids from inorganic and organic building
blocks to obtain greater control of the framework design.
(2), have been synthesized by a self-assembly reaction. Both of
5
2-
them contain an unexpected framework, Ag
topolopy, and the discrete M(en) 2
I
2 4
with tridymite
+
In 1997, Martin and Zubieta independently introduced a
new type of microporous compound, which utilized halide
3
cations are located in the
channels. Their thermal properties and circular dichroism spectra
were investigated.
6
ions as replacements for the oxygen or chalcogenide anions.
These materials were formed by transition-metal halides such
as zinc dichloride and cuprous chloride; zinc and copper are
both known to exhibit tetrahedral geometries with chlorine
atoms. These novel halozeotype materials represent non-
oxide analogues of microporous aluminosilicates and provide
the foundation for new developments in host-guest chem-
istry through crystal engineering of chemical framework
building units. However, few microporous halozeotype
materials have been reported so far.
Microporous materials are of great interest because of their
chemical diversity and immense practical importance for
commercial applications such as gas storage, ion exchange,
1
and catalysis. In the past decades, nature’s geological
examples have been followed by transforming commom
silicate, aluminate, and phosphate building blocks into
2
zeolite-type materials with microporous frameworks. There
are many elements that can be incorporated into the
frameworks to manipulate the chemical properties of the
materials. In spite of extensive substitution for the framework
composition, the known classes of microporous materials are
overwhelmingly dominated by oxide, mixed oxide/fluoride
matrices, or sulfides. The refractory nature of the metal
oxides provides remarkable stability to the microporous
frameworks at the expense of reactivity and tractability. For
To achieve a rational design of halozeotype materials, a
promising route is the choice of suitable inorganic composi-
tions as building units and flexible organic molecules as
templates. Recently, the reaction between silver iodide and
iodide ions attracted our attention because the solubility of
3
,4
AgI increases in appropriate solvents upon the addition of
-
excess KI and the active intermediate AgI
2
anion is a good
precursor to construct higher dimension compounds. Sig-
nificantly, the introduction of the metal complexes as
templates instead of organic amines has proven to be an
*
To whom correspondence should be addressed. E-mail: ylan@
dlut.edu.cn.
†
Department of Chemistry.
Department of Materials.
‡
(
1) (a) Chae, H. K.; Siberio-P e´ rez, D. Y.; Kim, J.; Go, Y.; Eddaoudi, M.;
(4) (a) Zones, S. I.; Darton, R. J.; Morris, R.; Hwang, S. J. J. Phys. Chem.
B 2005, 109, 652. (b) Villaescusa, L. A.; Barrett, P. A.; Camblor,
M. A. Angew. Chem., Int. Ed 1999, 38, 1997. (c) Bedard, R. L.;
Wilson, S. T.; Vail, L. D.; Bennett, J. M.; Flanigen, E. M. Stud. Surf.
Sci. Catal. 1989, 49, 375. (d) Parise, J. B. J. Chem. Soc., Chem.
Commun. 1990, 1553. (e) Cahill, C. L.; Ko, Y.; Parise, J. B. Chem.
Mater. 1998, 10, 19.
Matzger, A. J.; O’Keeffe, M.; Yaghi, O. M. Nature 2004, 427, 523.
(
b) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.;
O’Keeffe, M.; Yaghi, O. M. Science 2003, 300, 1127. (c) Pan, L.;
Liu, H.; Lei, X.; Huang, X.; Olson, D. H.; Turro, N. J.; Li, J. Angew.
Chem., Int. Ed. 2003, 42, 542. (d) Seo, J. S.; Whang, D.; Lee, H.;
Jun, S. I.; Oh, J.; Jeon, Y. J.; Kim, K. Nature 2000, 404, 982. (e)
Jung, O.-S.; Kim, Y. J.; Kim, K. M.; Lee, Y.-A. J. Am. Chem. Soc.
(5) (a) Pan, L.; Parker, B.; Huang, X.; Olson, D. H.; Lee, J. Y.; Li, J.
J. Am. Chem. Soc. 2006, 128, 4180. (b) Wang, X. L.; Qin, C.; Wang,
E. B.; Li, Y. G.; Su, Z. M.; Xu, L.; Carlucci, L. Angew. Chem. 2005,
44, 5824. (c) Dinca, M.; Yu, A. F.; Long, J. R. J. Am. Chem. Soc.
2006, 128, 8904–8913.
2002, 124, 7906. (f) Min, K. S.; Suh, M. P. J. Am. Chem. Soc. 2000,
122, 6834.
(
(
2) (a) Shin, D. M.; Lee, I. S.; Chung, Y. K. Cryst. Growth Des. 2006, 6,
1
059. (b) Qin, C.; Wang, X.; Carlucci, L.; Tong, M.; Wang, E.; Hu,
C.; Xu, L. Chem. Commun. 2004, 1876. (c) Parise, J. B. Inorg. Chem.
(6) (a) Martin, J. D.; Greenwood, K. B. Angew. Chem., Int. Ed. 1997, 36,
2072. (b) DeBord, J. R. D.; Lu, Y.; Warren, C. J.; Haushalter, R. C.;
Zubieta, J. Chem. Commun. 1997, 1375. (c) Martin, J. D.; Dattelbaum,
A. M.; Thornton, T. A.; Sullivan, R. M.; Yang, J.; Peachey, M. T.
Chem. Mater. 1998, 10, 2699. (d) Martin, J. D.; Yang, J.; Dattelbaum,
A. M. Chem. Mater. 2001, 13, 392.
1
985, 24, 4312. (d) Schnick, W.; Luecke, J. Angew. Chem. 1992, 104,
2
08. (e) Roca, M.; Marcos, M. D.; Amoros, P.; Beltran-Porter, A.;
Edwards, A. J.; Beltran-Porter, D. Inorg. Chem. 1996, 35, 5613.
3) (a) Bows, C. I.; Ozin, G. A. AdV. Mater. 1996, 8, 131. (b) Schnick,
W. Stud. Surf. Sci. Catal. 1994, 84, 2221.
3922 Inorganic Chemistry, Vol. 47, No. 10, 2008
10.1021/ic7025158 CCC: $40.75  2008 American Chemical Society
Published on Web 04/24/2008

COMMUNICATION
7
effective route to generating open-framework architectures.
Here we report two new framework complexes, 1 and 2,
which represent the first framework iodoargentates.
Both compounds 1 and 2 were prepared by dissolving
Zn(NO
mL of N,N-dimethylformamide (DMF). To the resulting
solution were added 1 mL of ethylenediamine and 3.8 g of
3
)
2
2
·6H O (0.089 g) or Ni(NO
)
3 2
2
·6H O (0.058 g) in
2
-
-
a 0.1 M AgI
2
/DMF solution. The 0.1 M AgI
2
/DMF
solution was prepared as follows: AgNO
3
(0.865 g) was
dissolved in 10 mL of DMF; the resulting solution was added
to 20 mL of the saturated KI/DMF solution and stirred until
the mixture became a clear solution; last, the solution was
diluted to 50 mL by the addition of DMF. The reactive
solution was kept at room temperature for 5 days, colorless
single crystals of 1 with 90% yield based on zinc and purple
single crystals of 2 with 93% yield based on nickel were
formed, and the products were washed with ethanol and
water, respectively. This synthetic route allowed us to obtain
a pure phase. The composition analyses of 1 and 2 by energy-
dispersive spectrometry indicate molar ratios of Zn:Ag:I )
Figure 1. Sheet of tetrahedra AgI4 viewed along the c axis showing a
sharing of the tetrahedra with alternating tetrahedral aprices pointing in the
opposite direction.
1
.0:2.1:4.1 and Ni:Ag:I ) 1.0:2.0:3.9, respectively, which
are in agreement with the results by X-ray diffraction
analyses below.
Single-crystal X-ray diffraction analyses of compounds 1
and 2 revealed that they are isomorphous and possess a three-
dimensional framework of AgI
topology. The Ag-I distances within the tetrahedral AgI
4
tetrahedra with tridymite
8
4
geometry range from 2.8529(10) to 2.890(3) Å, the I-Ag-I
angles vary between 104.93(6) and 113.88(5)°, and the
4
tetrahedral AgI is slightly distorted as compared with those
in other silver iodides.
The structures of compounds 1 and 2 can be viewed as
Figure 2. Structure of compound 1. Corner sharing of adjacent tetrahedra
9
sheets creates a three-dimensional framework with tridymite topology.
2
+
Zn(en)3 cations have been omitted for clarity.
built from the alternative stacking of two layers of AgI
4
tetrahedra along the c axis. In each layer, the tetrahedra share
three corners to form six-membered rings with alternating
tetrahedral aprices pointing up and down in the c direction,
as shown in Figure 1. The relationship between the two layers
is that all tetrahedra in one layer rotated by 37.59° about
the c axis with respect to one another. Corner sharing
between adjacent layers creates a three-dimensional frame-
2+
topology depicted in Figure 2. The discrete M(en)
are located in the six-membered channels.
3
cations
Thermogravimetric analyses (TGA) of compounds 1 and
were carried out under a flow of nitrogen (40 mL/min)
2
from 25 to 600 °C with a heating rate of 10 °C/min. The
curve for 1 shows multistep losses. The mass loss before
18 °C can be attributed to liberation of one organic ligand
weight loss: theoretical 6.2%; obsd 6.0%). In the following
step, 1 loses gradually the remaining organic ligands, and
this process overlaps with sublimation of ZnI ; therefore, it
2
(
4
work of all corner-shared AgI tetrahedra with tridymite
(
7) (a) Yang, G.; Sevov, S. C. Inorg. Chem. 2001, 40, 2214. (b) Wang,
Y.; Yu, J.; Guo, M.; Xu, R. Angew. Chem., Int. Ed. 2003, 42, 4089.
c) Wang, Y.; Yu, J.; Pan, Q.; Du, Y.; Zou, Y.; Xu, R. Inorg. Chem.
004, 43, 559. (d) Gray, M. J.; Jasper, J. D.; Wilkinson, A. P. Chem.
2
(
2
is difficult to make out these two thermal processes. The
total loss of 30.8% between 232 and 471 °C corresponds to
Mater. 1997, 9, 976. (e) Wang, Y.; Chen, P.; Li, J.; Yu, J.; Xu, J.;
Pan, Q.; Xu, R. Inorg. Chem. 2006, 45, 4764. (f) Chen, P.; Li, J.;
Duan, F.; Yu, J.; Xu, R.; Sharma, R. P. Inorg. Chem. 2007, 46, 6683.
8) Crystal data for 1: C6H24Ag2I4N6Zn, fw ) 969.02, monoclinic, P6(3),
a ) 9.0550(6) Å, b ) 9.0550(6) Å, c ) 14.4468(19) Å, γ ) 120.00°,
the loss of two organic amines and half of ZnI
2
(calcd: 12.4%
for 2 en and 16.5% for 0.5 ZnI ). The thermal decomposition
2
(
behavior of compound 2 is in a similiar pattern. It releases
organic ligands roughly in three steps with corresponding
mass losses of 2.6%, 3.1%, and 13.9%, respectively. The
total mass loss of 19.6% is in accordance with the theoretical
value of the complete loss of three organic ligands (calcd
3
-3
V ) 1025.84(17) Å , Z ) 2, Dcalc ) 3.137 g cm , R ) 0.0422, Rw
)
0.1027, reflections used 5740 with I > 2σ(I). Crystal data for 2:
C6H24Ag2I4N6Ni, fw ) 962.36, monoclinic, P6(3), a ) 8.9969(2) Å,
b ) 8.9969(2) Å, c ) 14.4374(7) Å, γ ) 120.00°, V ) 1012.06(6)
3
-3
Å , Z ) 2, Dcalc) 3.158 g cm , R ) 0.0360, Rw ) 0.0776, reflections
used 7767 with I > 2σ(I). Data collection was performed on a Bruker
Smart APEX II diffractometer equipped with graphite-mono-
chromitized Mo KR radiation (λ ) 0.710 73 Å) at 293 K.
1
8.6% for a loss of 3 en). The fourth loss of 19.9% from
(
9) (a) Li, H. H.; Chen, Z. R.; Li, J. Q.; Huang, C. C.; Zhang, Y. F.; Jia,
G. X. Cryst. Growth Des. 2006, 6, 1813. (b) Li, H. H.; Chen, Z. R.;
Li, J. Q.; Huang, C. C.; Zhang, Y. F.; Jia, G. X. Eur. J. Inorg. Chem.
430 to 525 °C is ascribed to the release of AgI.
2+
The circular dichroism (CD) spectra of M(en)
3
(M )
2
+
2+
2
006, 12, 2447.
Zn , Ni ) of compounds 1 and 2 in the visible region
Inorganic Chemistry, Vol. 47, No. 10, 2008 3923

COMMUNICATION
consist of two overlapping components of opposite sign.
Acknowledgment. We thank the National Natural Science
Foundation of China for financially supporting this work
(Grant 20671015).
These two CD spectra indicate D
3
symmetry of the complex
1
0
ions of zinc or nickel with chelating ethylenediamine.
In conclusion, two novel frameworks with tridymite
topology were successfully synthesized by a self-assembly
Supporting Information Available: X-ray crystallographic data
for compounds 1 and 2. The TGA data and CD spectra are shown
in Figures S1 and S2, respectively. This material is available free
of charge via the Internet at http://pubs.acs.org. CCDC 662863 and
-
reaction of AgI
2
and the corresponding metal complex ions
in a solution. The use of the metal complexes as templates
-
instead of organic amines causes condensation of AgI
2
to
2
-
three-dimensional open-framework Ag
2
I
4
. These results
6
662864 contain supplementary crystallographic data for 1 and 2,
provide a new avenue for the design and generation of new
solid-state materials based on the concept of using simple
clusters as building blocks to construct open-framework
structures.
respectively. The atomic coordinates for these structures have been
deposited with the Cambridge Crystallographic Data Centre. The
coordinates can be obtained, on request, from the Director,
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge, CB2 1EZ, U.K.
(
10) Cheetham, A. K.; Day, P. Solid State Chemistry: Techniques;
Cambridge University Press: Cambridge, U.K., 1987; p 172.
IC7025158
3924 Inorganic Chemistry, Vol. 47, No. 10, 2008