1
24
D.-Z. Wang et al. / Polyhedron 111 (2016) 123–131
obtained after filtering, washed with distilled water and dried in
air to produce the colorless crystals (ca. 30% yield based on L). Anal.
Calc. for C40 Zn: C, 50.66; H, 3.61N, 35.45. Found: C, 50.48;
H, 3.52; N, 35.65%. IR (cm , KBr pellets): 3394m, 3115m, 2526w,
34 24 2
H N O
L
ꢀ1
Chart 1. The structure of ligand L.
2416w, 2211w, 2081w, 1911w, 1871w, 1806w, 1522s, 1481s,
1318s, 1241s, 1148m, 1099m, 1064m, 1032m, 967m, 931m,
916m, 838m, 735m, 651m, 614m, 490m, 418m.
{
(
(
[ZnL(AcO)
AcO) ](CH
SO (H O)
2
](CH
3
CH
OH)}
O)}
2
OH)}
(5), {[CdL(H
(7). Interestingly, these compounds exhibit
1
(2), {[ZnL(H
2
O)
4
](SO
4 1
)} (3), {[CdL
2
3
CH
2
1
1
2
O) ](SiF
4
6
1
)} (6) and {[Cu
2 2
L
2
.3.2. {[ZnL(AcO)
A mixture of Zn(OAc)
.03 mmol) was dissolved in 15 mL ethanol and filtrated. The col-
2
](CH
3
CH
2
OH)}
1
(2)
4
)
2
2
2
](H
2
2
ꢁ2H
2
O (7 mg, 0.03 mmol) and L (7 mg,
various network architectures with a wide range from 0D to 2D
networks. The metal ions and the counter anions play important
roles in the construction of the final structures and their effects
will be discussed in detail. Furthermore, the luminescent property
and photocatalytic activity of the complexes 1–6 have been inves-
tigated and discussed, and complexes 1–5 exhibit photocatalytic
activity and selectivity for dye degradation under UV light.
0
orless block crystals were formed after several days with the evap-
oration of the filtrate. The crystalline product was obtained after
filtering and washed with methanol (ca. 40% yield based on L).
Anal. Calc. for C16
C, 43.60; H, 4.42; N, 19.21%. IR (cm , KBr pellets): 3267m,
20 6 5
H N O Zn: C, 43.50; H, 4.56; N, 19.02. Found:
ꢀ1
3165m, 3115m, 3061m, 3027m, 2975m, 2930m, 2890m, 2841m,
2649w, 2544w, 2419w, 2340w, 2301w, 2248w, 2001w, 1918w,
1621s, 1589s, 1538m, 1488m, 1454s, 1379s, 1328s, 1308m,
1265m, 1245m, 1168m, 1150m, 1122m, 1096m, 1049m, 1018m,
966m, 941m, 926m, 887m, 850m, 758m, 720m, 674m, 647m,
619m, 494m, 433m.
2
. Experimental
2
.1. Materials and general methods
All the other reagents used for the syntheses were commercially
available and employed without further purification. IR spectra
were measured on a Brucker Equinox 55 FT-IR spectrometer with
2
.3.3. {[ZnL(H
2
O)
4
](SO
4
)}
1
(3)
A mixture of ZnSO
4
ꢁ7H
2
O (7 mg, 0.02 mmol) and L (7 mg,
O: methanol = 2:
) and refluxed for 3 h. The colorless block crystals were formed
ꢀ1
KBr Pellets in the range of 4000–400 cm . Elemental analyses of
C, H and N were performed on a Thermo Flash EA 1112-NCHS-O
0
1
.03 mmol) was dissolved in 15 mL solvent (H
2
1
analyzer. H NMR data were collected using an INOVA-400 NMR
after several days with the evaporation of the filtrate. The crys-
talline product was obtained after filtering and washed with dis-
tilled water (ca. 40% yield based on L). Anal. Calc. for
C
3
2
1
4
spectrometer. Chemical shifts are reported in d relative to TMS.
The fluorescence behavior of ligand and their complexes were
studied using a Hitachi F-4500 Fluorescence Spectrophotometer
with a Xe arc lamp as the light source and bandwidths of 2.5 nm
at room temperature. UV–Vis absorption spectra were obtained
using a Hitachi UV-3010 UV–Vis spectrophotometer. The X-ray
powder diffraction (XRPD) was recorded on a Rigaku D/Max-
H
10 16
N
6
O
8
Zn: C, 29.03; H, 3.89; N, 20.31. Found: C, 29.65; H,
ꢀ1
.58; N, 18.76%. IR (cm , KBr pellets): 3175m, 3128m, 2356w,
026w, 1923w, 1806w, 1646m, 1581m, 1493s, 1453s, 1303s,
255m, 1069s, 967m, 929m, 834m, 760m, 645m, 616s, 532m,
94m, 444m.
2
500 diffractometer at 40 kV, 100 mA for a Cu-target tube and a
graphite monochromator.
2
.3.4. [CdL
The colorless crystals of 4 suitable for X-ray analysis were
obtained by the similar method described for 1, except for using
Cd(NO O instead of Zn(NO ꢁ6H O. (ca. 35% yield based on
ꢁ4H
L). Anal. Calc. for C40H34N24O Cd: C, 48.27; H, 3.44; N, 33.78. Found:
4 2
(OH) ] (4)
2.2. Preparation of ligand L
3
)
2
2
3
)
2
2
Imidazole (3.4 g, 49.9 mmol), sodium (1.2 g, 52.2 mmol) and
0 mL THF was added to a 250 mL three-necked flask. The solution
2
ꢀ
1
8
C, 48.70; H, 3.35; N, 33.65%. IR (cm , KBr pellets): 3419m, 3182m,
3133m, 3109m, 3062m, 2524w, 2397w, 2211w, 2081w, 1996w,
1910w, 1805w, 1521m, 1483s, 1455m, 1306m, 1239m, 1157w,
1100m, 1061m, 1032m, 967m, 926m, 827m, 752m, 646m, 617m,
490m, 421m.
was heated to reflux for 40 min. A solution of 3,6-dichloropyri-
dazine (3.7 g, 24.8 mmol) in THF (10 mL) was added to the mixture
within 40 min. The mixture was refluxed for 4 h under N . The
2
reaction mixture was poured into ice water mixture after cooled
to room temperature. The earthy yellow solid of L was obtained
after filtering. Pure ligand L was obtained by recrystallization from
2.3.5. {[CdL(AcO) ](CH CH OH)} (5)
2
3
2
1
1
ethanol as white crystals. Yield 80%. m.p. 281–282 °C. H NMR
Complex 5 was synthesized similarly as 2 by using Cd(OAc) ꢁ
2
(
8
DMSO-d
.11 (d, 2H, J = 2.4 Hz, imidazole-5), 7.23(d, 2H, J = 2.4 Hz, imida-
zole-4); Anal. Calc. for C10 : C, 56.60; H, 3.80; N, 39.60. Found:
C, 56.75; H, 3.75; N, 39.54%. IR (cm , KBr pellets): 3176w, 3145m,
6
): d: 8.69 (s, 2H, imidazole-2), 8.48 (s, 2H, pyridazine),
2H O instead of Zn(OAc) ꢁ2H O. (ca. 40% yield based on L). Anal.
2
2
2
16 20 6 5
Calc. for C H N O Cd: C, 39.32; H, 4.12; N, 17.19. Found: C,
ꢀ1
H
8
N
6
39.67; H, 4.98; N, 17.33%. IR (cm , KBr pellets): 3242m, 3183m,
3148m, 3129m, 3059m, 2975m, 2889m, 2840m, 2623w, 2486w,
2419w, 2321w, 1998w, 1918w, 1760w, 1683m, 1563s, 1535s,
1484s, 1455s, 1404s, 1311s, 1262m, 1166m, 1146m, 1118m,
1058s, 1034s, 967m, 931m, 883m, 843m, 760m, 744m, 674m,
648m, 618m, 495m, 428m.
ꢀ1
3109m, 3047m, 3018m, 2946m, 2782w, 2621w, 2526w, 2408w,
2214w, 1991w, 1903w, 1795w, 1727w, 1692w, 1645w, 1577s,
1519s, 1490s, 1459s, 1371s, 1321s, 1277s, 1237s, 1163m, 1106m,
1059m, 1031s, 962m, 903m, 861s, 823s, 766s, 749s, 645s, 613m,
507w, 487m, 421m.
2
.3.6. {[CdL(H
A mixture of CdSiF
.03 mmol) was dissolved in 15 mL solvent (H
2
O)
4
](SiF
6
)}
1
(6)
ꢁ6H O (7 mg, 0.02 mmol) and L (7 mg,
O: methanol = 1:1).
2
2
0
.3. Syntheses of complexes 1–7
6
2
0
2
.3.1. [ZnL
A mixture of Zn(NO
.3 mmol) and 5 mL water, which was placed in a Teflon-lined
4 2
(OH) ] (1)
The solution was refluxed for 3 h and allowed to evaporate for
seven days and finally suitable colorless block crystals were
formed. The crystalline product was obtained after filtering and
washed with distilled water (ca. 45% yield based on L). Anal. Calc.
3
)
2 2
ꢁ6H O (89 mg, 0.3 mmol) and L (63 mg,
stainless steel vessel (25 mL) was heated to 140 °C for 3 days, then
cooled to room temperature at a rate of 10 °C h . Complex 1 was
ꢀ1
16 6 4 6
for C10H N O F SiCd: C, 22.29; H, 2.99; N, 15.60. Found: C,