Chemistry - A European Journal
10.1002/chem.201700291
FULL PAPER
and more importantly makes one step further forward towards
the tetarpyrrole-based conjugated two-dimensional materials
with well defined composition and structure, nitrogen-containing
conjugated nature, tuneable central metal ions, and therefore
extensive application potentials.
MALDI-TOF MS: an isotopic cluster peaking at m/z 1357.23, Calcd. for
+
62 10 6 62 10 6
ZnC80H N O S, [M] 1356.88. Anal. Calcd. For ZnC80H N O S: C,
70.82; H, 4.61; N, 10.32. Found: C, 70.16; H, 4.90; N, 10.22.
Synthesis of 2,3,9,10,16,17-hexakis-(2,6-dimethylphenoxy)-23,24-
diaminophthalocyaninato zinc(II) [ZnPc(II)]: ZnPc(I) (67.8 mg, 0.05
mmol), nickel acetate tetrahydrate (50.5 mg, 0.2 mmol), and sodium
borohydride (12 mg, 0.3 mmol) were dissolved in a mixture of dried THF-
EtOH 1:2 (3 mL) at 0°C under nitrogen atmosphere. Two hours later the
reaction mixture was filtered over celite and the organic layer was
Experimental Section
General Remarks: THF were distilled from sodium. All other reagents
and solvents were used as received. The compounds of 4,5-di(2,6-
washed with NH
dried with NaSO
was purified by column chromatography using CHCl
3
4
Cl (2 M) and H
and concentrated under vacuum. The crude product
/THF (V/V, 9/1) as
2
O for two times. The organic layer was
4
[
32]
[36]
dimethylphenoxy)phthalonitrile,
5,6-dicyano-2,1,3-benzothiadiazole,
pyrene-4,5,9,10-tetraone, and
were prepared according to the published
2
,7-di-tert-butylpyrene-4,5-dione,
eluent, yielding 50.0 mg of diamino substituted ZnPc(II) (73.7%) as a
[
36]
hexaketocyclohexane
procedure.
dark blue powder after repeated chromatography followed by
1
recrystallization from THF and CH
3
OH. H NMR (THF-d
8
, 400 MHz): 8.32
(s, 2 H), 8.31 (s, 2 H), 8.15 (s, 2 H), 8.09 (s, 2 H), 7.46~7.26 (m, 18H),
1
2.42 (s, 36 H). UV/vis (THF): λmax[nm] (ε) = 349 (132 100), 611 (51 000),
H NMR spectra were recorded on a Bruker DPX 400 spectrometer.
Spectra were referenced internally using the residual solvent resonances
-
1
-1
6
1
8
75 (245 800), 689 (226 800 M cm ). IR (KBr): ν = 2951, 2919, 1610,
585, 1454, 1397, 1341, 1272, 1221, 1187, 1139, 1089, 1026, 890, 856,
relative to SiMe
4
. Electronic absorption spectra were recorded on a
-
1
13, 765, 746, 723, 508 cm . MALDI-TOF MS: an isotopic cluster
Lambda 750 spectrophotometer. IR spectra were recorded as KBr pellets
+
-
1
peaking at m/z 1331.05, Calcd. for ZnC80
Calcd. For ZnC80 : C, 72.20; H, 5.15; N, 10.52. Found: C, 72.88;
H, 5.05; N, 10.48.
68 10 6
H N O , [M] 1330.87. Anal.
using a Bruker Tensor 37 spectrometer with 2 cm resolution. MALDI-
TOF mass spectra were taken on a Bruker BIFLEX III ultra-high
resolution Fourier transform ion cyclotron resonance (FT-ICR) mass
68 10 6
H N O
-cyano-4-hydroxycinnamic acid as the matrix.
Elemental analyses were performed on an Elementar Vavio El III
elemental analyzer. Electrochemical measurements were carried out with
a BAS CV-50W voltammetric analyzer. The cell comprised inlets for a
glassy-carbon-disk working electrode with a diameter of 2.0 mm in
diameter and a silver-ware counter electrode. The reference electrode
was Ag /Ag (a solution of 0.01 M AgNO
which was connected to the solution by a Luggin capillary whose tip was
placed close to the working electrode. It was corrected for junction
potentials by being referenced internally to the ferrocenium/ferrocene
Synthesis of complex 1: A mixture of 2,7-di-tert-butylpyrene-4,5-dione
(6.88 mg, 0.02 mmol) and diamino substituted ZnPc(II) (26.6 mg, 0.02
mmol) in 1,4-dioxane (1 mL) and acetic acid (4 mL) was heated to reflux
under nitrogen atmosphere for
temperature, the volatiles were removed under reduced pressure and the
residue was purified by a silica gel column using CHCl as eluent. The
first green band containing the target complex 1 was collected. Repeated
chromatography followed by recrystallization from CHCl and CH OH
gave a purified product 1 (15.0 mg, 46.0%) as green powder. H NMR
(THF-d , 400 MHz): 10.14 (s, 2 H), 9.98 (s, 2 H), 8.57 (s, 2 H), 8.47 (s, 2
6 h. After being cooled to room
+
3
and 0.1 M TBAP in acetonitrile),
3
3
3
1
+
+
(
Fc /Fc) couple [E1/2(Fc /Fc) = 0.501 V vs. SCE]. Typically, a 0.1 M
8
solution of [NBu ][ClO ] in CH Cl /pyridine (V/V, 100/1) containing 1 mM
4
4
2
2
H), 8.19 (s, 2 H), 8.12 (s, 2 H), 8.08 (s, 2 H), 7.50~7.40 (m, 18H),
of sample was purged with nitrogen for 10 min, and then the
voltammograms were recorded at ambient temperature. The scan rates
were 100 and 20 mV/s for the CV and DPV measurement, respectively.
2.51~2.44 (m, 36 H), 1.81 (s, 18 H). UV/vis (THF): λmax[nm] (ε) = 355
(110 180), 627 (42 640), 696 (192 680), 717 (112 140 M cm ). IR (KBr):
ν = 2920, 2850, 1650, 1575, 1455, 1421, 1405, 1363, 1342, 1313, 1274,
-
1
-1
1
6
1
257, 1229, 1187, 1135, 1118, 1086, 1024, 987, 889, 860, 766, 747, 721,
-
1
52, 620, 576 cm . MALDI-TOF MS: an isotopic cluster peaking at m/z
Synthesis of 2,3,9,10,16,17-hexakis-(2,6-dimethylphenoxy)-23,24-
thiadiazolo[4,5-b]-phthalocyaninato zinc(II) [ZnPc(I)]: Mg (36.2 mg,
+
638.46, Calcd. for ZnC104
88 10 6
H N O , [M] 1639.29. Anal. Calcd. For
88 10 6
ZnC104H N O
: C, 76.20; H, 5.41; N, 8.54. Found: C, 75.99; H, 5.46; N,
1.5 mmol) in dry n-pentanol (2.0 mL) was heated to 150°C for 3 h under
8.50.
nitrogen atmosphere. After being cooled to room temperature, 4,5-
bis(2,6-dimethylphenoxy)phthalonitrile (552 mg, 1.5 mmol) and 5,6-
dicyano-2,1,3-benzothiadiazole (93 mg, 0.5 mmol) were added. The
mixture was heated at 150°C for 6 h. After being cooled to room
temperature, the volatiles were evaporated in vacuo and
trifluoroaceticacid (20 mL) was added. This reaction system was further
refluxed for 15 min. After filtration, the precipitate together with
Synthesis of complex 2: A mixture of 2,7-di-tert-butylpyrene-4,5,9,10-
tetraone (3.74 mg, 0.01 mmol) and diamino substituted ZnPc(II) (26.6 mg,
0.02 mmol) in 1,4-dioxane (1 mL) and acetic acid (4 mL) was heated to
reflux under nitrogen atmosphere for 8 h. After being cooled to room
temperature, the volatiles were removed under reduced pressure and the
Zn(OAc)
mixture was refluxed for another 4 h. After being cooled to room
temperature, CH OH (60 mL) was poured into the resulting green
solution. The precipitate was collected by filtration and chromatographed
on a silica gel column using CHCl as eluent. After the elution of the first
green band containing Zn[Pc(OC ], the second green band
containing the target thiadiazolo ZnPc(I) was collected. Repeated
chromatography followed by recrystallization from CHCl and CH OH
afforded ZnPc(I) as a dark blue powder, 121.3 mg (17.7%). H NMR
THF-d , 400 MHz): 8.44 (s, 2 H), 8.16 (s, 2 H), 8.10 (s, 2 H), 7.87 (s, 2
H), 7.47~7.12 (m, 18H), 2.42~2.38 (t, 36 H). UV/vis (THF): λmax[nm] (ε) =
2
·2H
2
O (315 mg, 1.5 mmol) was added into DMF (3 mL) and the
3
residue was purified by a silica gel column using CHCl /THF (V/V, 10/1)
as eluent. The first green band containing the target complex 2 was
collected. Repeated chromatography followed by recrystallization from
3
THF and CH
3
OH gave a purified product 2 (3.0 mg, 13.0%) as green
1
powder. H NMR (THF-d , 400 MHz): 10.65 (s, 4 H), 10.26 (s, 4 H), 8.61
8
3
8 9
H )
8
(s, 4 H), 8.21 (s, 4 H), 8.14 (s, 4 H), 7.49~7.46 (m, 36H), 2.54 (m, 72 H),
2.17 (s, 18 H). UV/vis (THF): λmax[nm] (ε) = 354 (114 900), 390 (90 900),
-
1
-1
416 (65 400), 443 (66 140), 633 (45 920), 704 (261 300 M cm ). IR
3
3
1
(KBr): ν = 2920, 2851, 1616, 1587, 1473, 1455, 1399, 1343, 1322, 1273,
-
1
(
8
1223, 1186, 1140, 1089, 1025, 893, 767, 747, 725 cm . MALDI-TOF MS:
an isotopic cluster peaking at m/z 2958.22, Calcd. for Zn
2
184 150 20 12
C H N O ,
-
1
-1
+
359 (120 100), 616 (103 600), 682 (268 600) 723 (344 800 M cm ). IR
20
[M] 2959.02. Anal. Calcd. For Zn2C184H150N O12: C, 74.56; H, 5.10; N,
(
1
KBr): ν = 2918, 2850, 1579, 1450, 1425, 1400, 1341, 1271, 1221, 1185,
138, 1095, 1036, 1018, 922, 893, 875, 766, 744, 719, 649, 511 cm .
9.45. Found: C, 74.49; H, 5.12; N, 9.41.
-
1
This article is protected by copyright. All rights reserved.