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Supporting information for
Coordination polymers based on square planar Co(II) node and linear spacer:
solvent-dependent pseudo-polymorphism and an unprecedented interpenetrating
structure containing both 2D and 3D topological isomers
Dong Mok Shin,a In Su Lee, b Young Keun Chung* a and Myoung Soo Lahc
a
Department of Chemistry and the Center for Molecular Catalysis, College of Natural
Sciences, Seoul National University, Seoul 151-742, Korea
b
Advanced Materials Research Institute, LG Chemical Ltd. Research Park, Taejon, 305-
380, Korea
c
Department of Applied Chemistry and Chemistry, College of Science and Technology,
Han Yang Unversity, Ansan 425-170, Korea
Synthesis of mppe. To a solution of LDA (generated in situ by the reaction of
diisopropylamine (1.8 ml, 12.8 mmol) in 30 ml of THF with n-BuLi (5.5 ml, 13.8
mmol) at -78 °C) was added 4-methyl pyrimidine (1.0 ml, 11 mmol) at -78°C. While the
solution was stirred at room temperature for 30 min, the solution turned to yellowish. To
the yellowish solution was added 4-acetyl pyridine (1.0 ml, 9.0 mmol) at room
temperature. The resulting solution was stirred for 4 h and quenched by addition of
water (30 ml) and methylene dichloride (30 ml). The methylene dichloride layer was
collected, evaporated to dryness, and dissolved in 15 ml of pyridine. The pyridine
solution was cooled to 0°C. Excess POCl3 (2 ml) was added dropwise to the pyridine
solution. The resulting solution was stirred at room temperature for 3h and quenched by
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addition of ice. After evaporation of pyridine, the residue was dissolved in water (30 ml)
and basified by addition of aqueous 4 M NaOH. Extraction with dichloromethane (100
ml) followed by chromatography on a silica gel column eluting with Et2O/MeOH (v/v,
10:1) gave 0.50 g of 5 (28 %). 1H NMR (CDCl3)  9.26 (s 1 H), 8.73 (d, 5.2 Hz, 1 H),
8.65 (d, 4.3 Hz, 2 H), 7.42 (2, 4.6 Hz, 2 H), 7.29 (d, 5.2 Hz, 1 H), 6.81 (s, 1 H) 2.62 (s, 3
H) ppm;
13
C NMR (CDCl3)  163.36, 158.95, 157.57, 150.88, 150.54, 127.09, 122.06,
121.13, 18.00; HRMS M+ calc. 197.0953, obsd. 197.0954.
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Discussion about the color change of 2 with/without the solvent:
The color change to blue might suggest desorption of the solvent followed by a
concomitant structural change from octahedral to tetrahedral. Usually this kind of
change may result in an overall change in the crystal. However, in our case, we could
not observe any changes in the XRD pattern before and after desorption of the solvent.
Thus, we imagine that a certain amount of cobalt metals are converted to a tetrahedral
geometry and a mixture of tetrahedral and octahedral cobalt ions coexists in the blue
crystal. If we assume that the change occurs in a small portion of the cobalt ions or a
newly formed phase is amorphous, the domain formed is not large enough to be
detected by the change in an XRD pattern. In these circumstances, we could only
observe the pre-existing crystalline phase, octahedral cobalt metals ions, even though
we could see only blue crystals by eye. A quite similar case was reported by Kitagawa et.
al. in Chem. Eur. J. 2002, 8, 3587. We also carried out TGA and DSC study. However,
we could not see any evidence for a special phase change or decomposition. We also did
an IR study in order to confirm whether the SCN ligand acts as a bridging ligand.
However, we did not find out any special indication.
(a)
(b)
Figure 1. Color change of the crystal 2. (a) Right after taking out the crystal. (b) 1 hr
later.
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X R P D s p e c tra o f 2
(a )
(b )
5
10
15
20
25
30
35
40
45
2 th e ta
Figure 2. Powder XRD spectra of 2. (a) in the solvent. (b) after 2days drying in 80oC .
50
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TGA of 2
3.5
3
weight
2.5
2
1.5
Solvent loosing region
1
0.5
0
0
50
100
150
200
250
300
350
400
450
o
Temp( C)
(a)
D S C of 2
1.5
1
0.5
0
0
20
40
60
80
100
-0.5
-1
-1.5
Tem p(o C )
(b)
Figure 3. (a) TGA of 2. (b) DSC of 2.
120
140
160
180
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Figure 4. IR spectrum of 2. CN stretching of SCN ligand at 2064 cm-1.