Inorganic Chemistry
Article
photoinduced decomposition of the chemical scavenger 1,3-
diphenylisobenzofuran (DPBF) that reacts readily with 1O2.
yield 41.0 mg, 26.7%. Anal. Calcd for C64H84N121Mg: C, 73.50; H, 8.10;
N, 16.07. Found: C, 73.27; H, 7.91; N, 16.00. H NMR (CDCl3, 400
MHz): δ 9.02 (d, J = 7.24 Hz, 4 H), 7.98 (t, J = 7.48 Hz, 4 H), 7.65 (d,
J = 7.72 Hz, 4 H), 4.30 (t, J = 7.26 Hz, 16 H), 1.83 (m, J = 7.31 Hz, 16
H), 1.44 (m, J = 7.39 Hz, 16 H), 0.88 (t, J = 7.34 Hz, 24 H). MS
(MALDI-TOF): m/z 1045.9 [M + H]+, 989.5 [M − C4H8]+. UV−vis
(CHCl3): λ/nm (10−5 M−1 cm−1) 745 (1.31), 670 (0.285), 489
(0.0648), 343 (0.549), 284 (0.349).
Synthesis of Metal-Free 1,8,15,22-Tetrakis(dibutylamino)-
phthalocyanine, H2{Pc[α-N(C4H9)2]4-C4} (1). Compound 2 (51.5
mg, 0.0492 mmol) was dissolved in CF3COOH (2 mL) and the
mixture stirred under a slow steam of nitrogen for 20 min. The
reaction mixture was then poured into cold water and neutralized with
ammonia solution. The precipitate was collected and washed several
times with CH3OH and then applied on an alkaline alumina column
with dichloromethane/petroleum ether (4/1) as eluent. Further
recrystallization from tetrahydrofuran and methanol afforded dark
green microcrystals of H2{Pc[α-N(C4H9)2]4-C4} (1): yield 33.7 mg,
66.9%. Anal. Calcd for C64H86N12: C, 75.11; H, 8.47; N, 16.42. Found:
C, 75.28; H, 8.26; N, 16.44. 1H NMR (CDCl3, 400 MHz): δ 9.02 (d, J
= 7.28 Hz, 4 H), 8.04 (t, J = 7.54 Hz, 4 H), 7.71 (d, J = 7.80 Hz, 4 H),
4.27 (t, J = 7.12 Hz, 16 H), 1.85 (m, J = 7.16 Hz, 16 H), 1.46 (m, J =
7.29 Hz, 16 H), 0.89 (t, J = 7.34 Hz, 24 H), 0.39 (s, 2H). MS
(MALDI-TOF): m/z 1023.9 [M + H]+, 966.8 [M − C4H8]+. UV−vis
(CHCl3): λ/nm (10−5 M−1 cm−1) 770 (1.19), 690 (0.346), 514
(0.0751), 340 (0.613), 285 (0.462).
Unsubstituted ZnPc was used as the reference compound (ΦΔ
=
0.56 in DMF). Steady-state fluorescence spectroscopic measurements
were carried out on an F4500 (Hitachi) instrument. The fluorescence
quantum yields (ΦF) were calculated following the published method
with H2Pc(t-Bu)4 as reference compound (ΦF = 0.77).15
Synthesis of 3-Aminophthalonitrile. 3-Nitrophthalonitrile (13.0
g, 75.1 mmol) was added to a mixture of methanol (230 mL) and
concentrated HCl (66.6 mL), and the suspension was heated to reflux.
To this mixture was added iron powder (12.7 g, 227 mmol) in small
portions over 2 h, and then the mixture was stirred vigorously for
further 1 h at the same temperature. The resulting mixture was then
poured into cold water and filtered through a Buchner funnel. The
̈
precipitate was washed with water, giving the target compound as a
yellow solid: yield 9.21 g, 85.7%. 1H NMR (CDCl3, 400 MHz): δ 7.40
(t, J = 3.38 Hz, 1H), 7.09 (d, J = 6.12 Hz, 1 H), 6.97 (d, J = 7.80 Hz, 1
H), 4.71 (s, 2 H). Mp: 195−197 °C. Anal. Calcd for C8H5N3: C,
67.12; H, 3.52; N, 29.35. Found: C, 67.19; H, 3.61; N, 29.33. IR
(KBr): νmax (cm−1) 3468, 3367, 1718, 1631, 1593, 1477, 1313, 1055,
798, 743, 417.
Synthesis of 3-Chlorophthalonitrile. 3-Aminophthalonitrile
(8.50 g, 59.4 mmol) was added to concentrated HCl maintained
below −5 °C. A solution of sodium nitrite (8.19 g, 87.0 mmol) in
water (18 mL) was added dropwise over 30 min, and then the mixture
was stirred for a further 30 min. To this mixture was added a solution
of CuCl (14.7 g, 148 mmol) in concentrated HCl (50 mL) dropwise
over 1 h. After toluene (200 mL) was added, the mixture was stirred at
80 °C for 1 h. After the mixture was cooled to room temperature, the
two layers were separated and the aqueous layer was extracted with
toluene, dried over Na2SO4, and filtered. After the solvent was
removed by evaporation under reduced pressure, the crude product
was chromatographed on a silica gel column using CH2Cl2 as eluent,
providing the target compound as a white solid: yield 4.03 g, 41.8%.
1H NMR (CDCl3, 400 MHz): δ 7.79 (d, J = 8.04 Hz, 1H), 7.74 (d, J =
Synthesis of 1,8,15,22-Tetrakis(dibutylamino)-
phthalocyaninato Nickel, Ni{Pc[α-N(C4H9)2]4-C4} (3). A mixture
of metal-free phthalocyanine 1 (40.5 mg, 0.0396 mmol), Ni(OAc)2·
4H2O (25.0 mg, 0.100 mmol), and 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU, 0.3 mL) in anhydrous n-pentanol (2 mL) was heated to reflux
for 6 h under nitrogen. After it was cooled to room temperature, the
mixture was evaporated to dryness under reduced pressure and the
residue was chromatographed on an alkaline alumina column using
dichloromethane as the eluent. The product was then further purified
by recrystallization from tetrahydrofuran and methanol, affording dark
green microcrystals of Ni{Pc[α-N(C4H9)2]4-C4} (3): yield 31.8 mg,
74.5%. Anal. Calcd for C64H84N12Ni·0.5CH2Cl2: C, 69.01; H, 7.63; N,
7.36 Hz, 1 H), 7.69 (t, J = 7.90 Hz, 1 H). Mp: 108−111 °C. Anal.
Calcd for C8H3N2Cl: C, 59.10; H, 1.86; N, 17.23. Found: C, 59.15; H,
1.73; N, 17.20. IR (KBr): νmax (cm−1) 3087, 1733, 1577, 1452, 1178,
1030, 942, 862, 800, 727, 549, 437.
1
14.97. Found: C, 69.08; H, 7.55; N, 15.09. H NMR (CDCl3, 400
MHz): δ 8.93 (d, J = 7.16 Hz, 4 H), 7.97 (t, J = 7.60 Hz, 4 H), 7.63 (d,
J = 7.72 Hz, 4 H), 4.16 (t, J = 7.08 Hz, 16 H), 1.81 (m, J = 7.27 Hz, 16
H), 1.44 (m, J = 7.34 Hz, 16 H), 0.88 (t, J = 7.34 Hz, 24 H). MS
(MALDI-TOF); m/z 1079.1 [M + H]+, 1022.9 [M − C4H8]+. UV−vis
(CHCl3): λ/nm (10−5 M−1 cm−1) 745 (1.05), 670 (0.285), 498
(0.0660), 331 (0.453), 289 (0.514).
Synthesis of 1,8,15,22-Tetrakis(dibutylamino)-
phthalocyaninato Zinc, Zn{Pc[α-N(C4H9)2]4-C4} (4). By employing
the procedure described above to prepare Ni{Pc[α-N(C4H9)2]4-C4}
(3) with Zn(OAc)2·2H2O (22.0 mg, 0.100 mmol) instead of
Ni(OAc)2·4H2O as starting material, pure Zn{Pc[N(C4H9)2]4-C4}
(4) was isolated as dark green microcrystals: yield 29.2 mg, 67.9%.
Anal. Calcd for C64H84N12Zn: C, 70.24; H, 7.86; N, 15.24. Found: C,
70.67; H, 7.59; N, 15.45. 1H NMR (CDCl3, 400 MHz): δ 9.03 (d, J =
7.24 Hz, 4 H), 7.99 (t, J = 7.44 Hz, 4 H), 7.66 (d, J = 7.68 Hz, 4 H),
4.31 (t, J = 7.16 Hz, 16 H), 1.83 (m, J = 5.32 Hz, 16 H), 1.44 (m, J =
5.90 Hz, 16 H), 0.88 (t, J = 7.26 Hz, 24 H). MS (MALDI-TOF): m/z
1085.3 [M + H]+, 1029.0 [M − C4H8]+. UV−vis (CHCl3): λ/nm
(10−5 M−1 cm−1) 746 (1.17), 674 (0.303), 489 (0.0648), 343 (0.549),
284 (0.349).
Synthesis of 3-(Dibutylamino)phthalonitrile. To a mixture of
3-chlorophthalonitrile (3.32 g, 20.4 mmol) and K2CO3 (5.65 g, 40.9
mmol) in DMF (30 mL) at 150 °C was added dibutylamine (7.95 g,
62.0 mmol). The resulting system was heated at the same temperature
for 6 h. After it was cooled to room temperature, the reaction mixture
was poured into water (100 mL) and extracted with petroleum ether,
dried over Na2SO4, and filtered. After the solvent was removed by
evaporation under reduced pressure, the crude product was chromato-
graphed on a silica gel column using dichloromethane/petroleum
ether (3/1) as eluent, giving the target compound as a yellow oil: yield
2.70 g, 51.8%. 1H NMR (CDCl3, 400 MHz): δ 7.41 (m, 1 H), 7.11 (d,
J = 7.36 Hz, 1 H), 7.07 (d, J = 8.88 Hz, 1 H), 3.42 (t, J = 7.66 Hz, 4
H), 1.59 (m, J = 7.20 Hz, 4 H), 1.34 (m, J = 7.43 Hz, 4 H), 0.97 (t, J =
7.36 Hz, 6 H). Anal. Calcd for C16H21N3: C, 75.26; H, 8.29; N, 16.46.
Found: C, 75.30; H, 8.20; N, 16.33. IR (KBr): νmax (cm−1) 2959, 2872,
2206, 1585, 1468, 1369, 1288, 1227, 1072, 945, 785, 554.
Synthesis of 1,8,15,22-Tetrakis(dibutylamino)-
phthalocyaninato Magnesium, Mg{Pc[α-N(C4H9)2]4-C4} (2). A
mixture of magnesium turnings (16.1 mg, 0.662 mmol) and a small
amount of iodine in anhydrous n-pentanol (3 mL) was refluxed for 1 h
under a slow steam of nitrogen. Then 3-(dibutylamino)phthalonitrile
(150 mg, 0.587 mmol) was added. The resulting mixture was refluxed
for another 11 h. After the mixture was cooled, the solvent was
evaporated. The crude product was chromatographed on an alkaline
alumina column with dichloromethane/methanol (200/1) as eluent,
affording the sample containing the four regioisomers of 1,8-/11,15-/
18,22-/25-tetrakis(dibutylamino)phthalocyaninato magnesium com-
plex as a green powder: yield 67.6 mg, 44.0%. This sample was then
recrystallized twice from tetrahydrofuran and methanol, giving dark
green microcrystals of pure 1,8,15,22-tetrakis(dibutylamino)-
phthalocyaninato magnesium isomer Mg{Pc[α-N(C4H9)2]4-C4} (2):
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Synthesis of 3-(dibutylamino)phthalonitrile, experimen-
1
tal and simulated isotopic patterns for 1−4, H NMR
spectra of 2−4, electronic absorption spectra of 1−4,
cyclic voltammograms of 1−4, absorption changes of 1,
F
Inorg. Chem. XXXX, XXX, XXX−XXX