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slowly. After completion of the addition, the mixture was stirred for
ca. 10 h with the system equipped with a drying tube. Then, the
solvent was evaporated completely under reduced pressure. The
residue was dissolved in diluted acetic acid solution (4 mol L–1,
100 mL), and the solution was left in a refrigerator at 0–4 °C for ca.
5 h and then filtered. A yellow solid was obtained and dried in
processed with CrysAlis RED (Oxford Diffraction Ltd., Version
1.171.35.21, release 20-01-2012, CrysAlis171.NET). The structures
were solved by direct methods (SHELXTL-97) and refined on F2 by
full-matrix last-squares techniques (SHELXTL-97).[14] All non-
hydrogen atoms were refined with anisotropic thermal parameters,
and all hydrogen atoms were included at calculated positions and
vacuo to give the primary product 1-(3-pyridyl)-3-phenyl-1,3- refined with isotropic thermal parameters in a riding model. The
propanedione (5.10 g).
crystal data and structure refinement for these complexes are sum-
marized in Table S1. Selected bond lengths and angles are given in
Table S2. CCDC 943718 (for 1), 943719 (for 2-NO3), 943720 (for 2-
BF4), and 943721 (for 2-ClO4) contain the supplementary crystallo-
3-(3-Pyridyl)-5-phenyl-1-H-pyrazole (HL3-p): 1-(3-Pyridyl)-3-
phenyl-1,3-propanedione (2.25 g, 0.01 mol) was added to ethanol
(50 mL), and the mixture was treated with excess hydrazine (80 %,
3 mL) and then heated under reflux for 10 h. The solution was left
in air to allow the evaporation of the ethanol solvent. After several
days, a nearly colorless microcrystalline solid was obtained and
dried in vacuo to afford the product (1.42 g, yield 64.3 %). IR (KBr):
Supporting Information (see footnote on the first page of this
article): Crystallographic details and additional measurements.
ν = 3400–3500 (s), 3161 (w), 3103 (w), 3020 (w), 2993 (w), 1631 (vs),
˜
1567 (s), 1375 (vs), 1176 (m), 1039 (m), 956 (m), 870 (m), 762 (s),
Acknowledgments
697 (s) cm–1 1H NMR (400 MHz, MeOD, 298 K): δ = 8.98 (s, 1 H,
.
CHpy), 8.44 (d, 1 H, CHpy), 8.23 (d, 1 H, CHph), 7.33–7.46 (m, 4 H,
CHph, CHpy), 7.08 (s, 1 H, CHpz) ppm.
This work is financially supported by the National Basic Re-
search Program of China (973 Program) (nos. 2013CB834803
and 2012CB821706), the National Natural Science Foundation
of China (nos. 21171114 and 91222202). S.-Z. Z. thanks the Na-
tional Natural Science Foundation of China (no. 21471094), the
Guangdong Natural Science Foundation (nos. S2013040012008
and 2014A030313477), and Shantou University for funding.
Ag(HL3-p)NO3 (1): A mixture of HL3-p (6.6 mg, 0.03 mmol), AgNO3
(5.1 mg, 0.03 mmol), and CH3OH (3 mL) was sealed in an 8 mL hard-
glass tube, which was heated in an oven at 120 °C for 72 h and
then slowly cooled to room temperature at a rate of –5 °C h–1. Col-
orless crystals were obtained. Yield: 55 % (based on ligand).
C14H11AgN4O3 (391.13): calcd. C 42.99, H 2.83, N 14.32; found C
43.01, H 2.61, N 14.35. IR (KBr): ν = 3420 (s), 3160 (w), 3101 (w),
˜
2965 (w), 1638 (vs), 1572 (vs), 1405 (s), 1169 (s), 1030 (m), 960 (m),
Keywords: Silver · N ligands · Argentophilic interactions ·
Luminescence · Sensors
830 (m), 792 (m), 713 (m) cm–1
.
[Ag3(HL3-3)2(NO3)3]n (2-NO3):
A mixture of HL3-3 (6.7 mg,
0.03 mmol), AgNO3 (10.2 mg, 0.06 mmol), and CH3OH (3 mL) was
sealed in an 8 mL hard-glass tube, which was heated in an oven at
120 °C for 72 h and then slowly cooled to room temperature at a
rate of –5 °C h–1. Colorless block crystals were obtained. Yield: 41 %
(based on ligand). C26H20Ag3N11O9 (954.11): calcd. C 32.73, H 2.11,
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N 16.15; found C 32.61, H 2.10, N 16.25. IR (KBr): ν = 3320 (m), 3150
˜
(w), 3004 (w), 1632 (s), 1562 (m), 1487 (vs), 1176 (w), 1125 (m), 955
(m), 823 (m), 695 (m), 532 (m) cm–1
.
[Ag3(HL3-3)2(ClO4)3]n (2-ClO4): A mixture of HL3-3 (6.7 mg,
0.03 mmol), AgClO4 (12.4 mg, 0.06 mmol), and CH3OH (3 mL) was
sealed in an 8 mL hard-glass tube, which was heated in an oven at
120 °C for 72 h and then slowly cooled to room temperature at a
rate of –5 °C h–1. Colorless crystals were obtained. Yield: 38 %
(based on ligand). C26H20Ag3N8Cl3O12 (1066.45): calcd. C 29.28, H
1.89, N 10.51; found C 29.31, H 1.91, N 10.55. IR data (KBr): ν = 3305
˜
(w), 3133 (w), 3080 (w), 1605 (m), 1462 (s), 1380 (s), 1090 (vs), 984
(m), 800 (s), 698 (s), 620 (s) cm–1
.
[Ag3(HL3-3)2(BF4)3]n (2-BF4):
A mixture of HL3-3 (6.7 mg,
0.03 mmol), AgBF4 (11.6 mg, 0.06 mmol), and CH3OH (3 mL) was
sealed in an 8 mL hard-glass tube, which was heated in an oven at
120 °C for 72 h and then slowly cooled to room temperature at a
rate of –5 °C h–1. Colorless crystals were obtained. Yield: 40 %
(based on ligand). C26H20Ag3N8B3F12 (1028.51): C 30.36, H 1.96, N
10.89; found C 30.21, H 1.91, N 10.85. IR (KBr): ν = 3346 (m), 3141
˜
(w), 3088 (w), 1605 (s), 1560 (m), 1458 (s), 1128 (s), 1082 (vs), 804
(vs), 694 (vs), 522 (m) cm–1
.
Crystal Structure Determination: The single-crystal X-ray data col-
lection for the complexes was performed with an Oxford Diffraction
Gemini
E diffractometer (Enhance Mo-Kα X-ray source, λ =
0.71073 Å) equipped with a graphite monochromator and an Atlas
CCD detector (CrysAlis CCD, Oxford Diffraction Ltd.). The data were
Eur. J. Inorg. Chem. 0000, 0–0
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