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T. Erdogan et al. / Journal of Photochemistry and Photobiology A: Chemistry 300 (2015) 6–14
7
non-fluorinated derivatives [34–36]. Therefore in this paper; we
have, in particular, combined these two functional materials into a
single compound and this time coumarin is substituted with
fluorine atom in the skeleton. We report here in this paper
synthesis, characterization, photophysical and photochemical
properties of novel peripheral and non-peripheral tetra 7-oxy-3-
(3,5-difluorophenyl) coumarin substituted zinc (II) Pcs (4 and 6)
and indium (III) Pcs (5 and 7) as potential PDT agents.
dissolved in dry dimethylformamide (DMF) (25 mL) under nitro-
gen and anhyd. K2CO3 (0.76 g, 5.49 mmol) was added after stirring
for 5 days at 50–60 ꢀC, the reaction mixture was treated with
diluted HCl under ice cooling. The crude product was filtered,
washed with water and dried. The product was purified by silica gel
column chromatography using CHCl3 as eluent.
Yield: 0.812 g (55%), mp: 268 ꢀC. IR (KBr tablet); nmax/cmꢁ1
3042–3084 (Ar C—H), 2231 (Ar—CN), 1699 (lactone, C O), 1606
(C = C), 1586–1460 (Ar C C), 1271 (Ar C—O) and 1122 (Ar C—F)
cmꢁ1 1H NMR (DMSO-d6), (
:ppm): 7.26 (dd, 1H, J = 8 and 2 Hz,
:
¼
¼
2. Experimental
.
d
Ar—H), 7.31 (t, 1H, J = 6 Hz, Ar—H), 7.38 (d, 1H, J = 2 Hz, Ar—H), 7.50
(dd, 2H, J = 8 and 2 Hz, Ar—H), 7.53 (dd, 1H, J = 8 and 2 Hz, Ar—H),
7.86 (dd, 1H, J = 8 and 2 Hz, Ar—H), 7.90 (d, 1H, J = 8 Hz, Ar—H), 7.96
(dd, 1H, J = 8 and 2 Hz, Ar—H), 8.46 (s, 1H, coumarin 4-H). MS
(MALDI-TOF), (m/z): 400.07 [M]+, 401.13 [M + H]+, 402.06 [M + 2H]+.
2.1. Materials and equipment
Unsubstituted zinc (II) phthalocyanine (ZnPc), 1,3-diphenyliso-
benzofuran (DPBF), Triton X-100, zinc(II) acetate [Zn(OAc)2],
indium (III) chloride (InCl3), potassium carbonate (K2CO3), sodium
acetate (NaOAc), 2,4-dihydroxybenzaldehyde and 3,5-difluoro-
phenylacetic acid were purchased from Aldrich. All solvents were
dried as described by Perrin and Armarego before use [37].
7-Hydroxy-3-(3,5-difluorophenyl) coumarin (1), 7-(2,3-dicyano-
phenoxy)-3-(3,5-difluorophenyl) coumarin (2) and 7-(3,4-
dicyanophenoxy)-3-(3,5-difluorophenyl) coumarin (3) were
synthesized and purified according to the literature procedures
[38].
C23H10F2N2O3: calcd. C, 68.94; H, 2.50; F, 9.49; N, 7.00%; found: C,
68.95; H, 2.46; F, 9.45; N, 7.02.
2.2.3. 7-(3,4-Dicyanophenoxy)-3-(3,5-difluorophenyl) coumarin (3)
Compound 3 was prepared and purified according to the
procedure described for 2, starting from compound 1 (1 g,
3.66 mmol), 4-nitrophthalonitrile (0.63 g, 3.66 mmol) and anhy-
drous K2CO3 (0.76 g, 5.49 mmol).
Yield: 0.925 g (62.90%), mp: 273 ꢀC. IR (KBr tablet); nmax/cmꢁ1
:
Infrared spectra (IR) were recorded on a Perkin Elmer Spectrum
100 FT-IR Spectrometer. Electronic absorption spectra were
recorded on a Shimadzu UV-2450 UV–visible Spectrophotometer.
Elemental analyses were performed by the Instrumental Analysis
Laboratory of the TUBITAK Marmara Research Centre. 1H NMR
spectra were recorded on a Varian Unity Inova 500 MHz NMR
Spectrometer. Mass spectra were performed on a Bruker Microflex
LT MALDI-TOF Spectrophotometer. Photo-irradiations were per-
formed using a General Electric quartz line lamp (300 W). A
600 nm glass cut off filter (Intor) and a water filter were used to
filter off ultraviolet and infrared radiations, respectively. An
interference filter (Intor, 670 nm with a band width of 40 nm)
was additionally placed in the light path before the sample. Light
intensities were measured with a POWER MAX5100 (Molelectron
detector incorporated) power meter.
3047–3084 (Ar C—H), 2230 (Ar—CN), 1699 (lactone, C
(C C), 1576–1454 (Ar C C), 1255 (Ar C—O) and 1120 (Ar C—F)
cmꢁ1 1H NMR (DMSO-d6), (
:ppm): 7.22 (dd, 1H, J = 8 and 2 Hz,
Ar—H), 7.31 (t, 1H, J = 6 Hz, Ar—H), 7.35 (d, 1H, J = 2 Hz, Ar—H), 7.51
(dd, 2H, J = 8 and 2 Hz, Ar—H), 7.59 (dd, 1H, J = 8 and 2 Hz, Ar—H),
7.86 (d, 1H, J = 8 Hz, Ar—H), 7.96 (d, 1H, J = 2 Hz, Ar—H), 8.17 (d, 1H,
J = 8 Hz, Ar—H), 8.48 (s, 1H, coumarin 4-H). MS (MALDI-TOF), (m/z):
400.03 [M]+, 401.10 [M + H]+, 402.07 [M + 2H]+. C23H10F2N2O3:
calcd. C, 68.94; H, 2.50; F, 9.49; N, 7.00%; found: C, 68.96; H, 2.43; F,
9.44; N, 7.04.
¼
O), 1603
¼
¼
.
d
2.2.4. General procedures for non-peripheral zinc (II) phthalocyanine
(4) and indium (III) chloride phthalocyanine (5)
A mixture of compound 2 (0.15 g, 0.375 mmol) and metal salt
[Zn(OAc)2 (0.017 g, 0.095 mmol), InCl3 (0.021 g, 0.095 mmol)] was
heated at 170 ꢀC with 4 mL dry 2-dimethylaminoethanol (DMAE) in
a sealed glass tube, and stirred for 24 h under a N2 atmosphere.
After cooling to room temperature, the green solution treated with
methanol (5 mL) and the product was filtered off and washed with
water, methanol and ethanol.
The photophysical and photochemical parameters were sup-
plied as Supplementary information.
2.2. Synthesis
2.2.1. 7-Hydroxy-3-(3,5-difluorophenyl) coumarin (1)
A mixture of 2,4-dihydroxybenzaldehyde (2 g, 14.5 mmol),
3,5-difluorophenylacetic acid (2.49 g, 14.5 mmol), anhydrous
NaOAc (1.78 g, 21.75 mmol) and 15 mL acetic anhydride was heated
with stirring at 160 ꢀC under nitrogen for 8 h. After removal of
acetic acid by distillation, the resulting mixture was treated with
10% HCl/methanol, and the precipitates were collected by
filtration. The dried product was purified by recrystallization from
methanol.
2.2.4.1.
1,8,15,22-Tetrakis[3-(3,5-difluorophenyl)-7-oxycoumarino]
phthalocyaninato zinc (II) (4). Yield: 0.066 g (42.31%),
mp > 300 ꢀC. IR (KBr tablet); nmax/cmꢁ1: 3060–3075 (Ar C—H),
1724 (lactone, C
(Ar C—O) and 1120 (Ar C—F) cmꢁ1. 1H NMR (DMSO-d6), (
6.99–8.44 (m, 40H, Ar—H). MS (MALDI-TOF), (m/z): 1665.20 [M]+,
1664.19 [M–H]+. UV/Vis (DMF) lmax/nm (log
): 690 (5.19),
621 (shoulder, 4.15), 340 (4.15). C92H40F8N8O12Zn: calcd. C,
66.28; H, 2.40; F, 9.12; N, 6.72; found: C, 66.32; H, 2.40; F, 9.11;
N, 6.78.
¼
O), 1602 (C
¼
C), 1508–1464 (Ar C
¼
C), 1239
d
:ppm):
e
Yield: 2.158 g (54.36%), mp: 275 ꢀC. IR (KBr tablet); nmax/cmꢁ1
3153 (—OH), 3040–3080 (Ar C—H), 1699 (lactone, C O), 1600
(C C),1591–1465 (Ar C
C) and 1120 (Ar C—F).1H NMR (DMSO-d6),
:ppm): 7.18 (dd, 1H, J = 8 and 2 Hz, Ar—H), 7.28 (t, 1H, J = 6 Hz,
:
¼
¼
¼
(d
2.2.4.2. 1,8,15,22-Tetrakis[3-(3,5 difluorophenyl)-7-oxycoumarino]
phthalocyaninato indium(III) chloride (5). Yield: 0.062 g (37.81%),
mp > 300 ꢀC. IR (KBr tablet); nmax/cmꢁ1: 3055–3075 (Ar C—H),1724
Ar—H), 7.32 (d, 1H, J = 2 Hz, Ar—H), 7.48 (dd, 2H, J = 8 and 2 Hz,
Ar—H), 7.83 (d, 1H, J = 8 Hz, Ar—H), 8.35 (s, 1H, coumarin 4-H), 9.32
(bs, 1H, —OH). MS (MALDI-TOF), (m/z): 274.04 [M]+, 275.08
[M + H]+, 276.11 [M + 2H]+. C15H8F2O3: calcd. C, 65.64; H, 2.92; F,
13.86%; found: C, 65.67; H, 2.89; F, 13.83.
(lactone, C
and 1120 (Ar C—F) cmꢁ1. 1H NMR (DMSO-d6), (
(m, 40H, Ar—H). MS (MALDI-TOF), (m/z): 1750.05 [M]+, 1714.55
[M–Cl]+. UV/Vis (DMF) lmax/nm (log
): 706 (5.25) 635 (shoulder,
¼
O), 1603 (C
¼
C), 1505–1479 (Ar C
¼
C), 1239 (Ar C—O)
d
:ppm): 7.03–8.43
e
2.2.2. 7-(2,3-Dicyanophenoxy-) 3-(3,5-difluorophenyl) coumarin (2)
4.25), 340 (4.15). C92H40F8N8O12InCl: calcd. C, 63.06; H, 2.28; F,
8.68; N, 6.40; found: C, 63.10; H, 2.28; F, 8.65; N, 6.48.
7-Hydroxy-3-(3,5-difluorophenyl)
3.66 mmol) and 3-nitrophthalonitrile (0.63 g, 3.66 mmol) were
coumarin
(1)
(1 g,