Article
Inorganic Chemistry, Vol. 48, No. 24, 2009 11661
In addition, the unsaturated metal sites have also been
exploited for reversible hydrogen storage studies, especially
in compounds containing transition elements.
Amino carboxylic acids are important in biology and can
have zwitterionic behavior. Researchers have employed the
amino carboxylic acids for designing new MOF structures.
5
10
Many of the reported MOF compounds were synthesized
The close structural relationship of the 5-aminoisophthalic
acid (AIP) to one of the well-explored benzene tricarboxylic
acids (trimesic acid) prompted us to investigate the reacti-
6
employing benzene polycarboxylic acids. Secondary organic
0
11
ligands, such as 4,4 -bipyridine, have also been used to
7
control the structure and dimensionality. Studies exploring
vity of AIP with transition metal ions. A search of the
12
the relative merits of the reaction time and temperature
literature revealed that the number of MOFs with 5-AIP
8
during the synthesis have also been investigated. A combi-
was not many in spite of the close resemblance to the trimesic
acid. We considered it important to explore the reactivity of
5-AIP with cobalt and nickel by varying a variety of reaction
parameters that include the time, the temperature, and the
solvent. Our efforts were successful, and we have isolated
four new 5-aminoisophthalate phases of cobalt and nickel.
The compounds, [M (C H NO ) (C H N )(H O) ] 3H O,
nation of the above studies has resulted in a bewildering
variety in the structures for the MOFs. To categorize and
catalogue the MOF structures, the node and net based
topological description using simple polyhedra and linkers
9
are being employed. This approach helped in understanding
the framework structures better and also helped in designing
new ones.
2
8
5
4 2
4
4
2
2
2
3
2
2þ
2þ
3
M = Co (I) and Ni (II) and [M (H O)(μ -OH) (C H -
NO )], M = Co (III) and Ni (IV), have been prepared
2
2
2
8
5
2þ
2þ
4
and characterized using a variety of techniques. The struc-
tures of I and II are related, having a bilayer two-dimensional
arrangement; the structures of III and IV have three-
dimensional structure that possesses one-dimensional M-
O(H)-M chains. We have also been able to demonstrate that
(
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the coordinated solvent molecules (H O) in compounds I and
2
(
6) (a) Kaye, S. S.; Long, J. R. J. Am. Chem. Soc. 2008, 130, 806–807.
II can be reversibly exchanged for D O. The fully hydrated
2
(
b) Karabach, Y. Y.; Kirillov, A. M.; Haukka, M.; Sanchiz, J.; Kopylovich, M. N.;
and dehydrated phases with the coordinatively unsaturated
metal sites have also been examined using the single crystal
to crystal transformation studies. In this paper, we present
the synthesis, structure, single crystal to single crystal trans-
formation studies, adsorption/desorption UV-vis, and
magnetic investigations on all of the compounds.
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Experimental Section
Synthesis and Initial Characterization. All of the compounds
were prepared by employing the hydro/solvothermal method.
The various synthesis conditions employed during the pre-
sent study are given in Table 1. In a typical synthesis for
[Co (C H NO ) (C H N )(H O) ] 3H O (I), Co(CH COO)
2 8 5 4 2 4 4 2 2 2 2 3 2
4H O (0.249 g, 1 mM) was dissolved in 10 mL of water. To this
2
were added 5-aminoisophthalic acid (0.181 g, 1 mM) and
pyrazine (0.040 g, 0.5 mM) under continuous stirring. The
mixture was homogenized for 30 min at room temperature,
transferred and sealed in a 23 mL PTFE lined autoclave, and
heated at 75 °C for 3 days under autogenous pressure. The final
product contained large quantities of single crystals, which were
filtered under vacuum, washed with deionized water, and dried
at ambient conditions. A similar procedure was adopted for all
of the compounds. In all cases, the products were found to
contain large quantities of single crystals along with micro-
crystalline powders. Thus, purple rod [Co (C H NO ) -
(
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(
2
8
5
4 2
(
C
4
H
4
N
2
)(H
NO
purple block [Co (H O)(μ -OH) (C H NO )] (III) (yield ∼
2
O)
2
] 3H
2
O (I) (yield ∼ 74%), light green rod
5
3
(
[Ni
2
(C
8
H
5
4
)
2
4
(C H
4
N
2
)(H O) ] 3H
2
2
3
2
O (II) (yield ∼ 63%),
3
2
2
2
8
5
4
3
4
65%), and light green block [Ni (H O)(μ -OH) (C H NO )]
2 2 2 8 5 4
(IV) (yield ∼ 67%) crystals were obtained (yields are based on
Co/Ni). Anal. Calcd for I: C, 37.17; H, 3.74; N, 8.67. Found: C,
(
(
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