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Dalton Transactions
Page 6 of 8
DOI: 10.1039/C8DT02275E
COMMUNICATION
Journal Name
9
5
6
mixture was stirred at 140
℃
for 48 h. After being cooled to 4H; H ), 8.11~8.14 (m, 8H; H ), 7.99 (d, J=8 Hz, 8H; H ), 7.58 (d,
J=8 Hz, 16H; H ), 7.19 (s, 2H; H ), 6.52~6.64 (m, 16H; H ), 4.73
2
8
1
room temperature, the solution was washed with acetone (15
mL) for 3 times to give a blue solid with yield about 17.5%. IR
7
s, 8H; H ), 4.35 (s, 8H; H ), 0.80~0.84 (s, 12H, H ), -0.03 (s, 4H;
H ); Anal. Calc. for C106H110N O Si): C, 68.15; H, 5.94; N,
12 18
9.00%. Found: C, 68.94; H, 5.92; N, 9.16%. ESI-MS m/z:
1238(Single substitution M=1238)
4
13
(
1
0
-1
ν
/cm : 3420, 2934, 1604, 1374, 1120, 857; Anal. Calc. for
172 176 16
H N O36Zn (3108): C, 66.45; H, 5.71; N, 7.21. Found: C,
C
+
6
6.97; H, 5.78; N, 7.58; ESI-MS m/z: 3238[M+4CH
Synthesis of di-3,5-di(4-methoxycarbonyl
benzyloxysilicon (IV) phthalocyanine (ME-SiPc)
3
OH] .
benzyloxy)
Photophysical properties
Fluorescence quantum yields (
F
Ф ) of dendrimer silicon
(
IV)/zinc phthalocyanines were determined in DMF by the
31,32
A mixture of SiPcCl
mmol), pyridine (1.5 mL) and methylbenzene (30 mL) was
stirred and refluxed at 140 for 24 h. The mixture was
2
(0.391 g, 0.64 mmol), D-ME (0.8729 g
,
2
comparative method using Eq. 1
.
F(std)
ФF =Ф ·F·AStd / (FStd ·A) (Eq. 1)
℃
Among them, F and FStd are the integral areas of emission
curves of dendrimer phthalocyanines and the standard,
unsubstituted ZnPc (n-ZnPc), respectively. A and AStd are the
absorbances of the dendrimer silicon (IV)/zinc phthalocyanines
allowed to cool to room temperature and filtered. The residue
was washed with dichloromethane (15mL) for 3 times. And
then the solvent was evaporated under reduced pressure.
Finally, the obtained solid was further purified on silica gel
chromatographic column using acetone/dichloromethane
and n-ZnPc at the excitation wavelengths, respectively. n-ZnPc
33
in DMF (ФF(std)=0.28) was employed as the standard .
(
v:v=1:200) as eluent to give a blue solid with yield about
-1
The fluorescence decay curve of dendrimer silicon (IV)/zinc
phthalocyanines were determined in DMF. Fluorescence
1
1
9
8
3
7.4%. IR v/cm : 3395, 2970, 1722, 1601, 1400~1500, 1338,
1
178, 1281, 1054, 888, 743; H NMR (400 MHz, CDCl
3
)
δ
/ppm:
8
9
.57~9.59 (m, 8H; H ), 8.24~8.26 (m, 8H; H ), 7.99 (d, J=8 Hz,
lifetime (τs) are obtained from fitting data to Eq. 2 .
e-t/
τ
1
e-t/
τ
2
τ
e-t/ 3
2
3
5
H; H ), 7.14(d, J=8 Hz, 8H; H ), 5.70 (s, 2H;H ), 4.11 (s, 8H; H ),
4
Fit=A+ B
The singlet oxygen quantum yield (
IV)/zinc phthalocyanines was calculated according to Eq. 3
1
+ B
2
+ B
3
(Eq. 2)
Φ ) of dendrimer silicon
Δ
1
6
7
.97 (s, 12H; H ), 3.54 (s, 4H; H ), -0.676 (s, 4H; H ); Anal. Calc.
14Si: C, 69.78; H, 4.43; N, 7.94%. Found: C, 70.07;
(
for C82
H
62
N
8
O
ref
and Eq. 4. n-ZnPc in DMF (ΦΔ =0.56) was employed as the
34
standard .
H, 4.48; N, 7.98%. MALDI-TOF-MS m/z: 976 [M].
Synthesis of di-{3,5-di-[4-(N-morpholinyl ethoxy) methoxycarbonyl
benzyloxy] benzyloxy silicon (IV)phthalocyanine (ME-ML-SiPc)
ref
ꢀ
ref
ꢀ
Φ
• k • I
Φ
ꢀ
=
ref
ꢀ
(Eq. 3)
k
•I
ꢀ
A mixture of ME-SiPc (0.035 g, 0.025 mmol), 2- morpholine
ethanol (3 mL) and pyridine (0.15 mL) was stirred and refluxed
0
at 140 C for 24h. After the mixture was allowed to cool to
ref
ref
a
− A670
I
1−10
=
(Eq. 4)
−A
670
I
a
1−10
room temperature
, acetone (100 mL) was added. Then the
ref
Among them, Φ
quantum yield of n-ZnPc in DMF; k and k
photobleaching constant of measured phthalocyanine and n-
Δ
=0.56 indicates that the singlet oxygen
reactant was filtered and the supernatant was collected. After
the solvent was removed, the residue was re-solubled in
petroleum ether. Then the supernatant was collected and the
solvent was removed. Finally, the obtained solid was further
purified on silica gel chromatographic column using
dichloromethane as eluent for two times to obtain a blue solid
ref
are the
ref
ZnPc in DPBF, respectively; I
a
and I
a
indicated that the
absorption rates of dendrimer phthalocyanines and n-ZnPc
with the excitation of 670 nm respectively.
-1
The constant of photoinduced electron transfer (k ) in DMF
et
with yield about 44.7%. IR v/cm : 3442, 2856, 2929, 2956,
1
722, 1601, 1446, 1379, 1281, 1172, 1116, 1071, 844, 758; H
can be calculated from the fluorescence lifetime data using eq
1
1
2
5, in which τ is the fluorescence lifetime of SiPcCl , while τ is
0
2
x
3
NMR (400 MHz, CDCl ) δ/ppm: 9.56~9.65 (m, 8H; H ),
1
.34~8.37 (m, 8H; H ), 8.03~8.05 (d, J=8 Hz, 8H; H ), 7.48~7.52
1
5
the value of short-lived component for measured dendrimer
silicon (IV)/zinc phthalocyanine. The fluorescence lifetime of
8
6
8
m, 8H; H ), 6.62 (s, 2H; H ), 5.30~5.36 (m, 8H; H ), 4.45~4.64
7
(
(
(
2
8
4
m, 8H; H ), 3.71~3.73 (m, 8H; H ), 2.56~2.78 (m, 16H; H ), 0.38
3
1
2 0
SiPcCl in DMF (τ = 5.51ns) was obtained .
-
1
-1
2
9
10
k =τ - τ0
et
(Eq. 5)
x
s, 16H; H ), -0.71 (s, 4H; H ), -1.91 (s, 4H, H ). Anal. Calc. for
18Si: C, 67.76; H, 5.46; N, 9.30%. Found: C, 67.87; H,
Efficiency for photointroduced electron transfer (Φet) was
2
calculated by using the ket value according to Eq. 6 .
(Eq. 6)
102 98 12
C H N O
8
+
2
5.51; N, 9.37%. MALDI-TOF-MS m/z: 1228[M+3H O] (M=1174).
Φ
et = ket·τ
x
Synthesis of di-{3,5-di-[4-(N-iodomethylated morpholinyl ethoxy)
methoxycarbonyl benzyloxy] benzyloxy silicon (IV) phthalocyanine
(
ME-MLI
A mixture of ME-ML-SiPc (0.0362 g, 0.012 mmol) and
idomethane (CH I) (5 mL) was stirred and refluxed at 45 for A series of axial and peripheral substituted morpholinyl
4
-SiPc)
Conclusions
3
℃
overnight. And the mixture was filtered and washed with dendrimer phthalocyanines have been synthesized. Their
1
chloroform, ether and acetone, respectively. Finally,
structures were characterized by IR, HNMR and ESI-MS as well
-
1
ME-MLI
1
4
-SiPc was obtained. IR ν/cm : 3425, 2945, 2882,
as MALDI-TOF mass methods. The water solubility of these
dendrimer phthalocyanines exhibited morpholinyl group
number dependence. ME-ML-ZnPc exhibited better water
1
725, 1632, 1466, 1239, 1131, 1069, 950, 883, 758; H NMR
1
400 MHz, DMSO-d6) δ /ppm: 9.60~9.73 (m, 8H; H ),
2
(
8
3
.98~9.00 (d, J=8 Hz, 8H; H ), 8.55~8.59 (m, 8H; H11), 8.32 (s,
6
| J. Name., 2012, 00, 1-3
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