4
438
V. Mantareva et al. / European Journal of Medicinal Chemistry 46 (2011) 4430e4440
ꢀ
1
ammonium hydroxide (25%) was added to the reaction mixture
and stirring was continued overnight. After the water phase was
evaporated the residue was diluted with DMF. The mixture was
poured into 400 mL of water and the precipitate obtained was
collected by filtration, washed thoroughly with DMF:water (1:2),
with water only and then with Ac. The crude product was chro-
(0.42), 365 (0.84). IR (KBr):
n
, cm ¼ 3058, 1614, 1574, 1500, 1472,
1424, 1405, 1347, 1320, 1237 (CeOeC), 1123, 1086, 1055, 1022, 954,
810, 749, 734, 707, 644. H (600 MHz, DMSO-d (ppm): 9.48e9.59
(m, 4H), 8.98e9.06 (m, 4H), 8.76e8.82 (m, 4H), 8.61e8.63 (m, 4H),
8.05e8.15 (m, 4H), 7.86e7.93 (m, 4H), 7.61e7.68 (m, 4H). Calc. for
52 30 12 6
C H N O Ge: C 62.99, H 3.05, N 16.95%; Found: C 62.54, H 3.08, N
1
6
) d
þ
þ
matographed on silica gel using CH
greenish impurities. The desired compound was then eluted as
a blue band using CH Cl :MeOH (2:1). After solvent evaporation
a second chromatography was applied using CHCl and then
CHCl :MeOH (9:1) to get rid of impurities. Finally, the product was
eluted with CHCl :MeOH (6:4). Removal of the solvent resulted in
.578 g of blue solid. Yield: 54%. M ¼ 946.97 g mol . UVeVis
2
Cl
2
to remove first yellow and
16.26%. ESI-MS (positive ion mode) m/z: 992 [M] , 974 [M ꢀ H
2
O] .
2
2
4.3.6. Synthesis of 2(3),9(10),16(17),23(24)-tetrakis-[3-(N-methyl)
pyridyloxy]-phthalocyaninato dihydroxygermanium (IV) tetraiodide
(GePc1) (mixture of regioisomers)
3
3
3
A quantity of 100 mg (0.1 mmol) of dihydroxygerman-
ꢀ
1
0
ium 2,9,16,23-tetrakis-(3-pyridyloxy)phthalocyanine (GePc2) was
dissolved in dry DMF (10 mL). An excess of methyl iodide (5 mL,
80 mmol) was added and the solution was stirred for 16 h under
5
(
DMF)
l, nm (
3
/10 ): 676 (0.56), 608 (0.13), 345 (0.29). IR (KBr): n,
ꢀ
1
cm ¼ 3058, 1614, 1574, 1519, 1472, 1412, 1331, 1238 (CeOeC),
1
ꢁ
1
(
4
125, 1079, 1060, 1021, 956, 820 (SieOH), 758, 734, 706, 538.
600 MHz, DMSO-d (ppm): 9.50e9.64 (m, 4H), 8.98e9.07 (m,
H), 8.75e8.81 (m, 4H), 8.61e8.62 (m, 4H), 8.05e8.14 (m, 4H),
Si: C
H
nitrogen at 50 C. The methyl iodide was evaporated and the
6
)
d
reaction product was precipitated with CH
and washed with CH Cl , EtOH and Ac. The compound was dis-
solved in water and after filtration isolated by freeze-drying cycle.
2 2
Cl (400 mL), filtered off
2
2
7.85e7.92 (m, 4H), 7.62e7.67 (m, 4H). Calc. for C52
H
30
N
12
O
6
ꢀ
1
6
5.95, H 3.19, N 17.74%; Found: C 65.74, H 3.23, N 17.21%. ESI-MS
Yield: 138 mg (88%). M ¼ 1559.25 g mol , UVevis (H
2
O, pH 7, SDS
/10 ): 678 (0.33), 643 (0.52), 613(0.48). IR (KBr):
, cm ¼ 3024, 2941 (CH ), 2831 (CH ), 1613, 1582, 1500, 1469,
1405, 1385 (CH ), 1346, 1275 (CeOeC), 1217, 1122, 1089, 1056, 966,
ꢀ
ꢀ1
5
(
negative ion mode) m/z: 946 [M ].
0.1 mol L
n
)
l, nm (
3
ꢀ
1
3
3
4
.3.4. Synthesis of 2(3),9(10),16(17),23(24)-tetrakis-[3-(N-methyl)
pyridyloxy]-phthalocyaninato dihydroxy-silicon (IV) tetraiodide
SiPc1) (mixture of regioisomers)
(3),9(10),16(17),23(24)-Tetrakis-(3-pyridyloxy)phthalocyani-
nato dihydroxy-silicon (IV) (SiPc2) in a quantity of 150 mg
0.158 mmol) was dissolved in DMF (10 mL). An excess of methyl
3
1
6
887, 742, 663. H (600 MHz, DMSO-d ) d (ppm): 10.0e9.6 (m, 2H),
9.6e9.34 (m, 5H), 9.34e9.12 (m, 2H), 9.12e8.93 (m, 4H), 8.93e8.75
(m, 4H), 8.75e8.58 (m, 2H), 8.58e7.9 (m, 9H), 4.70e4.26 (m, 12H).
(
2
42 12 6 4
Calc. for C56H N O GeI : C 43.12, H 2.72, N 10.78%; Found: C
(
42.85, 2.92, 10.85%. ESI-MS (positive ion mode) m/z: 263
[M ꢀ 4I ] , 236.6 [M ꢀ 4Iꢀ ꢀ Ge(OH)
ꢀ
4þ
þ 2H ]
þ 4þ
.
iodide (2 mL, 32 mmol) was added and the solution was stirred for
2
ꢁ
1
9 h under nitrogen at 50 C. The rest of methyl iodide was evap-
orated and the reaction product was precipitated with CH
filtered off and washed with CH Cl , EtOH and Ac. The compound
was dissolved in water and after filtration isolated by freeze-drying.
2 2
Cl ,
4
.4. Steady state and time-resolved fluorometry
2
2
ꢀ
1
The fluorescence emission spectra were recorded at excitation
wavelength 610 nm for the spectral region of 625e750 nm by using
cm quartz cuvette (Hellma) at RT. The fluorescence quantum
yields ( ) were calculated on the basis of absorption and fluores-
Yield: 200 mg (83%). M ¼ 1514.73 g mol . UVeVis (H
2
O, pH 7, SDS
/10 ): 675 (1.24), 642 (0.61), 609(0.18),
ꢀ
1
5
0
.1 mol L
)
l, nm (
3
ꢀ
1
1
3
1
46(0.56). IR (KBr):
n
, cm ¼ 3026, 2941 (CH
3 3
), 2830 (CH ), 1614,
F
F
582, 1501, 1471, 1409, 1330, 1275(CeOeC), 1124, 1083, 1061, 966,
1
cence spectra of SiPc1 and GePc1 and by using a comparative
method [28]. The equation (1) was employed for calculations:
8
26(SieOH), 756, 663, 541. H (600 MHz, DMSO-d
m, 2H), 9.66e9.70 (m, 2H), 9.38e9.47 (m, 8H), 8.98e9.00 (m, 4H),
.63e8.70 (m, 4H), 8.30e8.38 (m, 8H), 4.49 (s, 6H), 4.47 (s, 6H).
Calc. for C56 SiI : C 44.39, H 2.80, N 11.10%; Found: C 43.69,
H 2.99, N 11.26%. ESI-MS (positive ion mode) m/z: 251.3 [M ꢀ 4I ]
6
) d: 9.73e9.77
(
8
ꢀ
ꢁ.ꢀ
ꢁ
2
42
H N
12
O
6
4
F
F
¼
F
FðRÞ I AðRÞ
h
I
ðRÞ
A
h
2
(1)
ð Þ
R
ꢀ
4þ
.
where
F
F(R) is the fluorescence yield of the reference standard
4
.3.5. Synthesis of 2(3),9(10),16(17),23(24)-tetrakis-(3-pyridyloxy)
(ZnPc, F
F(R) ¼ 0.18 in DMSO [42]), I and I(R) are the integrated
phthalocyaninato dihydroxygermanium (IV)(GePc2) (mixture of
regioisomers)
fluorescence of the sample (SiPc1 or GePc1) and the reference
standard (ZnPc), A and A(R) are the absorbance of the sample and
Dry 4-(3-pyridyloxy)-1,3-diiminoisoindoline (2) (0.400 mg,
the reference, and h and h(R) are the refractive indices of the
1
.68 mmol) was placed in a 100 mL two-necked round-bottomed
flask, equipped with magnetic stirrer and a reflux condenser. A
freshly distilled quinoline (10 mL) was added to the flask and 0.5 mL
solvents employed in calculating of fluorescence quantum yields.
The absorbances of the sample and the reference were kept under
0.05 at
lexc in order to avoid the reabsorption effect.
of GeCl
4
(4.29 mmol) was transferred with the aid of syringe under
The fluorescence lifetimes (
s
F
) of SiPc1 and GePc1 and the used
ꢁ
ꢁ
inert gas atmosphere at RT. The reaction was stirred at 200 C for
standard ZnPc were measured at 20 C in 1 cm quartz cuvette with
a stopper by the means of an SPEX Fluorolog-3 fluorometer (Horiba
Jobin Yvon). The time-correlated single photon counting (TCSPC)
mode of the apparatus equipped with the Fluorolog fitting software
IBH program was used. Briefly, the set-up consists of the excitation
source (light emitting diode NanoLED, 365 nm) with 1 MHz repeti-
tion rate with a linear polarizer. The fluorescence was detected by
a peltier cooled photomultiplier tube (PMT) and the integrated
electronics. A monochromator with a spectral width of 2 nm was
used to select the required emission wavelength band. The response
function of the system, which was measured with a scattering Ludox
solution (DuPont), had a full width at half-maximum (FWHM) of
about 500 ps for NanoLED. All decay curves were measured at the
emission maximum of PSs and the lifetimes were obtained by
2
h. The formation of a green precipitate took place. After being
cooled 20 mL of water solution of ammonium hydroxide (25%) and
0 mL of pyridine was added to the reaction mixture and stirring
was continued overnight. The reaction mixture was poured into
00 mL of water and the green precipitate obtained was collected
2
5
by filtration, washed thoroughly with DMF:water (1:2) with water
only and then with Ac. The crude product was dissolved in
a mixture of CH
initially CH Cl :MeOH (9:1) to remove first impurities. The desired
compound was then eluted as blue-green band using
CH Cl :MeOH (6:4). Removal of the solvent resulted in deep-blue
solid. Yield (with respect to the phthalonitrile used): 1.29 g (77%).
2 2
Cl :MeOH and chromatographed on silica gel using
2
2
a
2
2
ꢀ
1
5
M ¼ 991.50 g mol . UVeVis (DMF)
l
, nm ( /10 ): 680 (1.93), 612
3