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BULLETIN OF THE
ISSN (Print) 0253-2964 | (Online) 1229-5949
KOREAN CHEMICAL SOCIETY
M
L
M
L
M
L
2
+
3+
2+
3+
2+
2+
3+
3+
M = Fe , Fe , Co , Co , Ru , Mn , Mn , Cr
L =
C
C
-
,
CN,N
N , N
N, CN
NC, N
N
2
2-
2-
2-
2-
=
Pc , TPP , taa , Hp , TBP
Figure 1. Schematic drawing of the bridged macrocyclic transition-metal compounds [MacML]n.
in this experiment were used as received from Aldrich Chemi-
cals Co. Ltd. All solvents, namely tetrahydrofuran, xylene,
alcohol, and toluene, etc., were dried over anhydrous materials
because moisture affects the reactions.
the molecular formula C H N SiCl . The blue-purple pow-
32 16 8 2
der product after being washed with quinoline, benzene, meth-
ꢀ
anol, and acetone was dried at 110 C and weighed 10.46 g
(63% yield based on 1,3-diiminoisoindoline).
Instruments. Fouriertransform infrared(FT-IR)spectrawere
recorded on a Nicolet 510P spectrophotometer using KBr pel-
lets and measured from 4000 to 400 cm . Si-NMR spectra
were recorded on a Solid State NMR spectrometer (Varian
Unity, Palo Alto, CA, USA) at 300 MHz (Si frequency
μ-(Dimethylsilane)phthalocyaninatosilicon, [PcSi(dms)]
.
n
Synthesis of [PcSi(dms)] was based on the method of Bur-
n
−1 29
11
khard ofthedehalogenationofdiorganodichlorosilaneswith
metallic sodium. Dichlorophthalocyaninatosilicon (3.06 g,
5 mmol) was added to a dispersed solution of metallic sodium
(0.3 g) usedas a dechlorinating agent in xylene (20 mL) under
121.42 MHz) for solid samples. UV–vis spectra were
ꢀ
recorded on an UV-365 spectrophotometer (Shimadzu Co.,
Kyoto, Japan) by using Nujol mull between quartz plates.
Elemental analyses were performed with a CE instrument
EA-1110 elementary analyzer at the combustion temperature
nitrogen at 110 C, and dichlorodimethylsilane (0.97 g,
7.5 mmol) was slowly dropped into the mixture solution with
vigorous stirring. It was maintained for 48 h at reflux temper-
ature. After removing xylene under reduced pressure and fil-
ꢀ
of 1300 C, and He gas was used as the carrier gas. Mass spec-
tering, the product was washed with concentrated H SO and
2 4
tra were recorded with a JMS-DX 303 mass spectrometer
distillated water, and then purified centrifugally in n-hexane
several times. The compound was dried at 110 C for 10 h.
ꢀ
(
JEOL Co., Akishima, Japan) at the ionization temperature
ꢀ
of 220 C and electron energy of 70 eV. Thermogravime-
try/differential thermal analysis (TG/DTA) measurements
were carried out with a TG-DTA-92 thermal analyzer
Dark blue powder. Anal. Calcd for C34
H N Si
22 8 2
(M = 598.77): C, 68.20; H, 3.70; N, 18.71. Found: C,
−
1
67.13; H, 3.49; N, 17.94. IR (KBr, cm ): 1611, 1517 (Si-
Pc), 1288, 1256*, 1163, 1066, 1077, 908, 834*, 803*,
783, 727, 528, 417. UV–vis (nujol, λmax nm): 692 (Q-band),
(
SETARAM Co., Caluire, France) and conducted under a
ꢀ
nitrogen atmosphere at the heatingr rate of 10 C/min. Electri-
cal conductivity values were recorded on a Keithley 195A dig-
ital multimeter (Cleveland, OH, USA) in the four-probe
geometry on compact powders pressed by 1 ton.
29
367 (B-band).
−204.7 (Si-Pc).
Si-NMR (ppm) δ = −24.9 (Si-CH ),
3
μ-(Diphenylsilane)phthalocyaninatosilicon, [PcSi(dps)] .
n
Synthesis of Dichlorophthalocyaninatosilicon, PcSiCl2.
Dichlorophthalocyaninatosilicon as the starting material used
for the syntheses of bridged phthalocyaninatosilicon com-
The synthetic procedures of [PcSi(dps)]
and [PcSi(mps)]
n n
were similar to those of [PcSi(dms)] . Dichlorophthalocyani-
n
natosilicon: 0.77 g, 1.27 mmol; Dichlorodiphenylsilane:
1.2 mL, 6.35 mmol; Metallic sodium: 0.13 g. Dark green-
pounds [PcSi(L)] (L = dms, dps, and mps) was prepared
n
10
by a modification of the procedure reported in the literature.
blue
powder.
Anal.
Calcd
for
C H N Si
44 26 8 2
Dichlorophthalocyaninatosilicon was obtained from 1,3-
diiminoisoindoline with silicon tetrachloride by heating. In
a three-necked flask equipped with a water condenser, a
mechanically stirred mixture of 16.3 g (0.11 mol) of 1,3-dii-
minoisoindoline, 40.5 mL (0.16 mol) of silicon tetrachloride,
(M = 722.91): C, 73.10; H, 3.62; N, 15.50. Found: C,
−1
72.22; H, 3.38; N, 14.84. IR (KBr, cm ): 1608, 1531,
1471, 1462*, 1524*, 1335, 1289, 1121, 1101*, 1079, 1060,
1050 (broad), 910 (Si-N), 617, 573, 564, 530. UV–vis (nujol,
29
λ
max nm): 744 (Q-band), 378 (B-band). Si-NMR (ppm)
δ = −98.5 (Si-ꢀ), −225.0 (Si-Pc).
ꢀ
and 185 mL of quinoline was reacted at reflux 219 C under
nitrogen. It was maintained at this temperature for 30 min and
then cooled to 184 C and filtered (Whatman no. 541). The
μ-(Methylphenylsilane)phthalocyaninatosilicon,
[PcSi
ꢀ
(mps)] . Dichlorophthalocyaninatosilicon: 0.6 g, 1 mmol;
n
molecular ion peak at m/z 611 in the mass spectrum indicated
Dichloromethylphenylsilane: 8.25 mL, 5 mmol, Metallic
Bull. Korean Chem. Soc. 2016, Vol. 37, 207–212
© 2016 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.bkcs.wiley-vch.de
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