Article
BULLETIN OF THE
ISSN (Print) 0253-2964 | (Online) 1229-5949
KOREAN CHEMICAL SOCIETY
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analyses (TGA) were performed at a scan rate of 5 C/min
using a Seiko TG/DTA 320 & SSC 5200H Disk Station
system (Seiko Instruments Inc., Tokyo, Japan). Luminescence
spectra were obtained with a SCINCO FS-2 fluorescence
spectrometer (SCINCO Co. Ltd., Seoul, Korea).
(Tmin/Tmax = 0.8945).8 The crystal structures of 1–3 were
solved by direct methods,9 and refined by full-matrix least-
squares refinement using the SHELXL-2013 computer pro-
gram.10 The positions of all non-hydrogen atoms were refined
with anisotropic displacement factors. All hydrogen atoms
were placed using a riding model, and their positions were
constrained relative to their parent atoms using the appropriate
HFIX command in SHELXL-2013. The crystallographic
data and the result of refinements of 1–3 are summarized in
Table 1.
Crystallographic data for the structures reported here have
been deposited with CCDC (Deposition No. CCDC-994985
(1), CCDC-994986 (2), and CCDC-994987 (3)). These data
Cambridge CB2 1EZ, UK, E-mail: deposit@ccdc.cam.ac.uk.
Preparation of [Ag(tpmd)](NO3)ꢀ2CH3OH (1). To an ace-
tonitrile solution (3 mL) of AgNO3 (12 mg, 0.071 mmol) was
added a mixture solution (MeOH/MeCN, 1:2, v/v, 3 mL) of
tpmd (25 mg, 0.071 mmol). After stirring for 10 min at room
temperature, MeOH (3 mL) was added to the mixture. Then
the mixture solution became transparent, and stirred for
10 min at room temperature. Colorless crystals of 1 were
obtained by diffusion of diethyl ether into the colorless solu-
tion for several days in a dark place, washed with MeOH, and
dried in air. Yield: 27 mg (65%). IR (KBr, cm−1): 3432, 3047,
1585, 1499, 1365, 1219, 1046, 814, 594. Anal Calcd for
C21H23AgN7O5.5: C, 44.30; H, 4.07; N, 17.22. Found: C,
44.34; H, 3.78; N, 17.44.
Results and Discussion
Preparation of [Ag(tpmd)](CF3SO3) (2). To an acetonitrile
solution (3 mL) of AgCF3SO3 (18 mg, 0.071 mmol) was
added a mixture solution (MeOH/MeCN, 1:2, v/v, 3 mL) of
tpmd (25 mg, 0.071 mmol). The resulting solution was stirred
for 10 min at room temperature, and then 3 mL of MeOH was
added to the mixture. The solution became colorless and was
stirred for 10 min at room temperature. Colorless crystals of
2 were obtained by diffusion of diethyl ether into the colorless
solution for several days in a dark place, washed with MeOH,
and dried in air. Yield: 20 mg (46%). IR (KBr, cm−1): 3446,
3100, 3048, 1855, 1503, 1367, 1262, 1030, 852, 635. Anal
Calcd for C22H19AgF3N6O3.5S: C, 42.59; H, 3.09; N,
13.55; S, 5.17. Found: C, 42.40; H, 2.97; N, 13.64; S, 5.02.
Preparation of [Ag(tpmd)](CF3CO2)ꢀ0.5CH3OH (3). To a
methanol solution (3 mL) of AgCF3CO2 (16 mg,
0.071 mmol) was added a methanol solution (2 mL) of tpmd
(25 mg, 0.071 mmol). The resulting solution was stirred at
room temperature for 10 min, and then 1 mL of MeCN was
added to the mixture. The solution became colorless and
was stirred for 10 min at room temperature. Colorless crystals
of 3 were obtained by diffusion of diethyl ether into the color-
less solution for several days in a dark place, washed with
MeOH, and dried in air. Yield: 23 mg (53%). IR (KBr,
cm−1): 3434, 3051, 16896, 1586, 1501, 1366, 1202, 1048,
815, 593. Anal Calcd for C23H23AgF3N6O4.5: C, 44.53; H,
3.74; N, 13.55. Found: C, 44.65; H, 3.39; N, 13.73.
X-ray Crystallographic Data Collection and Refinement.
Crystals of 1–3 were mounted on a CryoLoop® (Hampton
Research, Aliso Viejo, CA, USA) with Paratone® oil (Chev-
ron Oronite Pte Ltd Korea Branch, Seoul, Korea). Intensity
data for all structures were collected with a Bruker APEX
CCD-based diffractometer (Korea Basic Science Institute,
Chonju Branch) and using Mo Kα radiation
(λ = 0.71073 Å, graphite monochromator) at 200(2) K. The
raw data were processed to give structure factors using the
Bruker SAINT program and corrected for Lorentz and polar-
ization effects.7 The intensity data of 3 were corrected for
absorption using the SADABS program with multi-scan data
Synthesis and Characterization. Coordination polymers
−
−
1–3 were prepared from AgX (X = NO3 , CF3SO3 ,
−
CF3CO2 ) and tpmd ligand in mixed solvent (CH3OH/
CH3CN) at room temperature, respectively (Scheme 1). The
coordination networks are obtained in good yields and charac-
terized by EA, IR, and X-ray crystallography. 1–3 are slightly
soluble in water, but insoluble in acetone, CH3OH, and
Me2SO, and also sensitive to light. The IR spectrum of 1 in
KBr pellet shows a strong band of the nitrate ion at
1365 cm−1 and displays CH peak corresponding to the pyri-
dine groups at 3047 cm−1.11 The IR spectrum of 2 exhibits
strong absorption at 1262 and 635 cm−1 that is assigned to
the triflate ions as counterion and displays CH peaks corre-
sponding to the pyridine groups at 3048 cm−1.11 The IR spec-
trum of 3 in KBr pellet shows a strong band of the
trifluoroacetate ion at 1686 cm−1 and exhibits CH peak corre-
sponding to the pyridine groups at 3051 ꢂcm−1.11 TGA of
1 showed a weight loss of 10.3% at 100 C, which corre-
sponds to the loss of all solvent molecules per unit formula
(Figure S1, Supporting Information); no chemical decompo-
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sition was observed up to 200 C. It was shown that the major
weight loss (64.5%, 200–326 C) is due to degradation of the
tpmd ligand. Further chemical decomposition was not
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observed between 326 and 500 C, in which the final product
is expected to be AgNO3. TGA of 2 showed that no solvents
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were included and decomposition starts at 260 C (Figure S2).
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Between 260 and 451 C, the main weight loss (56.2%) is
shown due to degradation of the tpmd. The resulting weight
was almꢂost constant over the temperature range of
451–500 C, in which the remaining product is regarded as
AgCꢂF3SO3. TGA of 3 showed a weight loss of 6.5% at
100 C, which corresponds to the loss of all solvent molecules
per unit formula (Figure S3); no chemical decomposition was
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observed ꢂup to 170 C. The major weight loss (59.3%,
170–316 C) was observed and was attributed to decomposi-
tion of the tpmd. However, no chemical decomposition was
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observed between 316 and 500 C, in which the resulting
Bull. Korean Chem. Soc. 2016, Vol. 37, 19–26
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