Synthesis and optical/electrochemical properties of meso-5,10,15,20-tetrathienyl substituted porphyrins and their metal complexes

Article abstract of DOI:10.14233/ajchem.2015.17089

Two kinds of meso-5,10,15,20-tetrathienyl substituted porphyrin compounds, meso-5,10,15,20-tetra(2-thienyl)porphyrin (H₂TTP), meso-5,10,15,20-tetra(3-methyl-2-thienyl)porphyrin [H₂T(3-M)TP] and their metal complexes were synthesized and characterized by IR, ¹H NMR. UV-visible absorption spectra, fluorescence spectra, photoluminescence spectra and the cyclic voltammograms of the synthesized porphyrins and metalloporphyrins. Optical properties reveal that zinc porphyrin possesses intensive fluorescence emission, whereas cobalt(II) and copper(II) porphyrins exhibit no fluorescence emission. When the complexation of H₂TTP and H₂T(3-M)TP with metal ions occur, the electrochemical band-gaps (Eg) increase meanwhile the E_LUMO shows smaller change than that of the E_HOMO. The values of ionization potential, electronic affinity, HOMO energy level (E_HOMO) and LUMO energy level (E_LUMO) of the synthesized porphyrins and metalloporphyrins were also given in the paper.

Full text of DOI:10.14233/ajchem.2015.17089

Asian Journal of Chemistry; Vol. 27, No. 2 (2015), 616-620
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2015.17089
Synthesis and Optical/Electrochemical Properties of meso-5,10,15,20-Tetrathienyl
Substituted Porphyrins and Their Metal Complexes
*
YONG ZHOU, FUDE LIU , HAIYAN WU, BOYANG QU and LIJIE DUAN
Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, School of Chemistry & Chemical Engineering, Tianjin University
of Technology, Tianjin 300384, P.R. China
*
Corresponding author: E-mail: liufude@tjut.edu.cn; 15202206925@126.com
Received: 21 January 2014;
Accepted: 25 April 2014;
Published online: 10 January 2015;
AJC-16631
Two kinds of meso-5,10,15,20-tetrathienyl substituted porphyrin compounds, meso-5,10,15,20-tetra(2-thienyl)porphyrin (H
2
TTP), meso-
1
T(3-M)TP] and their metal complexes were synthesized and characterized by IR, H
5
,10,15,20-tetra(3-methyl-2-thienyl)porphyrin [H
2
NMR. UV-visible absorption spectra, fluorescence spectra, photoluminescence spectra and the cyclic voltammograms of the synthesized
porphyrins and metalloporphyrins. Optical properties reveal that zinc porphyrin possesses intensive fluorescence emission, whereas
2 2
cobalt(II) and copper(II) porphyrins exhibit no fluorescence emission. When the complexation of H TTP and H T(3-M)TP with metal
ions occur, the electrochemical band-gaps (Eg) increase meanwhile the ELUMO shows smaller change than that of the EHOMO. The values of
ionization potential, electronic affinity, HOMO energy level (EHOMO) and LUMO energy level (ELUMO) of the synthesized porphyrins and
metalloporphyrins were also given in the paper.
Keywords: Porphyrin, Metalloporphyrin, Electrochemical properties, Optical properties, Zn(II), Co(II), Cu(II).
In recent years, metal prophyrins have been proved to be
of great interest as photosynthetic model compounds in light-
INTRODUCTION
8,9
In the past decades, great efforts have been made to the
design and synthesis of new conjugated polymers due to their
energy conversion applications ; polythiophenes have been
widely used in the polymer based solar cells (PSCs) as electron
10
donors . In this paper, we have synthesized a series of comp-
1, 2
unique optoelectronic properties in organic devices . For
polymer based solar cells, the power conversion efficiency
needs to be further improved before commercialization,
although conjugated polymers based devices have achieved
lexes of thiophene-porphyrins and their metal complexes in
order to make better use of the advantages of porphyrins for
preparing a low band-gap polythiophenes. The optical and
electrochemical properties of the compounds are reported
consequently.
3
over 9 % recently . One of the main efforts for this is to obtain
new polymers with low band-gap (Eg) (as the donor materials),
which is the key parameter to enhance the efficiency of photon
4
absorption and improve the power conversion efficiency .
EXPERIMENTAL
Porphyrins have attracted much attention due to their wide
use in nature as one kind of tetrapyrrolic macrocycles with
big π-orbital on the carbon-nitrogen framework, such as chloro-
phyll, haem and cytochrome, each consisted of tetrapyrrole
2-Thiophenecarboxaldehyde, 3-methylthiophene and
pyrrole were purchased from Aladdin. Propanoic acid, DMF,
3
POCl , nitrobenzene and all other solvents and chemicals used
in this work were analytical grade and purchased from commer-
cial sources without further purification before use. Column
chromatography was carried out on silica gel (200-300 mesh).
2+
3+
5
compounds and Mg , Fe ions etc . Because of the rigid flat
structure and large conjugational effect of the tetrapyrrolic
macrocycle, the energy gap between the highest occupied
molecular orbital (HOMO) and the lowest unoccupied
molecular orbital energy (LUMO) is relatively small, which
leads to strongly absorption in the range of 400-700 nm with
high molar absorbance coefficient and effective charge-transfer
1
13
H NMR spectra and C NMR were recorded on a Bruker
AM-400 spectrometer using CDCl as solvent in all cases. FT-
3
IR analyses were performed on a Nicolet 380 spectrometer.
UV-visible spectra and fluorescene spectra of the polymers
were measured by HITACHI U-3310 spectrophotometer and
HITACHI F-4500 fluorescence spectrophotometer, respec-
6,7
efficiency .

Vol. 27, No. 2 (2015)
Synthesis and Optical/Electrochemical Properties of meso-5,10,15,20-Tetrathienyl Substituted Porphyrins 617
tively. Photoluminescence experiments were performed on a
FL3-212-TCSPC fluorescence spectrophotometer. Cyclic
voltammogram (CV) measurements were conducted on an
electrochemistry workstation (LK-2005A, Tianjin) with the
compound film on platinum (Pt) plate as the working electrode,
Pt wire as counter electrode andAg/AgCl electrode as a reference
electrode with a scan rate of 50 mV/s. Tetrabutyl ammonium
perchlorate (TBAP, 0.1 mol/L) and chloroform were used as
supporting electrolyte and solvent, respectively. The measure-
ments were calibrated using ferrocene as standard.
extracted by diethyl ether 3 times. The organic layer was
washed with saturated sodium carbonate solution and water
4
and then dried with anhydrous MgSO . After the solvent was
evaporated, dark red liquid as crude product was obtained.
The crude product was distillated under vacuum to collect 7.7 g
product (yield 61 %, 68-70 °C, 0.35 KPa, light yellow liquid).
1
3
H NMR (CDCl , 400 MHz): 10.042 (s, 1H), 7.633-7.645 (d,
1H), 6.971-6.983 (d, 1H), 2.586 (s, 3H).
meso-5,10,15,20-Tetra(2-thienyl)porphyrin (compound
2
2, H TTP): 30 mL glacial acetic acid, 30 mL propionic acid
The synthetic routes of the meso-5,10,15,20-tetrathienyl
substituted porphyrins and their metal complexes are shown
in Scheme-I.
and 15 mL of nitrobenzene were added into a 250 mL four-
neck flask and the solution was heated under reflux at about
130 °C for 20 min. 2.8 mL (0.03 mol) 2-thiophenecarboxal-
dehyde in 30 mL propionic acid was added dropwise, mean-
while 2.07 mL (0.03 mol) of freshly distilled pyrrole in 30 mL
acetic acid was added dropwise.After refluxing for 50-55 min,
the reaction mixture was cooled to ambient temperature natu-
rally. Then 25 mL of methanol was added, the solution was
allowed to standing overnight. The precipitate was filtered and
washed with hot water and ethanol for 3-4 times until the filtrate
was nearly colorless. After drying for 24 h under vacuum, 2.1
g of purple powder was obtained as crude product. The crude
product was purified by silica gel column chromatography
3
-Methyl-2-thiophenecarboxaldehyde (compound 1):
9.62 mL (0.1 mol) 3-methylthiophene and 14 mL of anhydrous
DMF were added into a 50 mL four-neck flask. The solution
was cooled to 10 °C below by an ice-bath, 10.2 mL (0.11 mol)
3
of POCl was added slowly. After the addition, the cooling
bath was removed and the reactant was stirred at ambient
temperature for 1.5 h. The solution was refluxed until 3-methyl-
thiophene was found disappeared by means of TLC. Then,
the reaction mixture was poured into 25mL of ice water,
adjusted to pH 5-6 with 40 % sodium hydroxide solution and
S
CH3
CH3
CH3
CHO
CH3
N
POCl3
NH N
N HN
S
H
S
S
DMF
S
S
H C
3
1
H C
3
S
NH N
N HN
3
S
CHO
S
S
N
H
S
S
2
N
N
N
CHCl /CH OH
3
S
3
M
2
M(OAc) ·nH O
2
2
S
N
4
. M = Zn n = 2
1
. M = Cu n = 1
5
2
. M = Co n = 4
6
S
3
S
CH3
CH3
S
CHCl /CH OH
3
N
N
3
S
M
3
M(OAc) ·nH O
2 2
N
N
7
8
9
. M = Zn n = 2
1
. M = Cu n = 1
CH3
2
. M = Co n = 4
3
S
H C
3
Scheme-I: Synthetic routes for the compounds of meso-5,10,15,20-tetrathienyl substituted porphyrins and their metal complexes

618 Zhou et al.
Asian J. Chem.
(chloroform/petroleum ether = 2:1), then 0.9 g desired blue-
purple compound 2 was obtained (yield 18.8 %, mp. > 300 °C).
RESULTS AND DISCUSSION
-1
2 2
The IR spectra of H T(3-M)TP and H TTP show that the
IR (KBr, νmax, cm ): 3321, 3096, 2918, 2850, 1806, 1628,
1
stretching vibrational absorption peak of N-H bond in pyrrole
553, 1468, 1396, 1073, 1041, 967, 950, 794, 707, 632, 521.
-1
1
ring is at about 3321 cm and the bending vibrational absor-
H NMR (CDCl
H), 7.878-7.894 (d, 4H), 7.522-7.543 (m, 4H), -2.626 (s, 2H).
meso-5,10,15,20-Tetra(3-methyl-2-thienyl)porphyrin
compound 3, H T(3-M)TP]: meso-5,10,15,20-Tetra(3-
methyl-2-thienyl)porphyrin was synthesized in the similar way
as H TTP with a yield of 16.5 %, m.p. > 300 °C. IR (KBr, νmax
3
, 400 MHz): 9.064 (s, 8H), 7.941-7.952 (d,
-1
ption peak of the N-H bond is at about 967 cm . When the
complexation of H T(3-M)TP and H TTP with metal ions
4
2
2
occur, the two absorption peaks mentioned above disappear,
which indicates that the bond between N-H in pyrrole ring is
substituted by N-metal ions. This is the typical characteristic
[
2
2
,
-1
of the formation of metalloporphyrin complexes.
1
cm ): 3321, 3095, 2920, 2851, 1647, 1545, 1460, 1334, 1056,
1
67, 795, 709, 617, 469. H NMR (CDCl , 400 MHz): 8.938
3
2 2
H NMR spectra of H TTP and H T(3-M)TP show that
9
the chemical shift of the synthesized two kinds of porphyrin
derivatives present negative position at -2.626 and -2.617,
respectively, which can be attributed to the chemical shift of
(
s, 8H), 7.741-7.758 (d, 4H), 7.338-7.358 (d, 4H), 2.118-2.202
m, 12H), -2.617 (s, 2H).
(
Zinc meso-5,10,15,20-tetra(2-thienyl)porphyrin
compound 4, ZnTTP): A mixture of compound 2 (0.14 g,
2 2
H in bond N-H. When the complexation of H TTP and H T(3-
(
M)TP with metal ions occur, the corresponding peaks at nega-
1
tive position disappear, such as H NMR of ZnTTP and ZnT(3-
0
.22 mmol) and Zn(OAc)
2 3
(0.072 g, 0.33 mmol) in CHCl
(20 mL) and CH OH (6 mL) was refluxed for 2 h.After cooling
3
M)TP. This indicates that the H in bond N-H is replaced by
metal ions, meanwhile metal complexes of porphyrin formed.
1
Owing to the paramagnetism, H NMR of CuTTP, CuT(3-
to room temperature, the mixture was filtered and washed with
water. After drying for 24 h under vacuum, the crude product
was purified by the silica gel column chromatography
M)TP, CoTTP and CoT(3-M)TP can not be measured in this
1
work. In comparison with the H NMR of H
(chloroform: petroleum ether = 1:1), then 0.126 g desired blue-
purple compound 4 was obtained (yield 82 %, m.p. > 300 °C).
2
TTP, H T(3-M)TP,
2
-1
ZnTTP and ZnT(3-M)TP, we find that the chemical shift
slightly decreases in compound H T(3-M)TP, which is possibly
IR (KBr, νmax, cm ): 3096, 2921, 2851, 1633, 1487, 1425,
1
350, 1291, 1167, 1072, 972, 798, 702, 466. H NMR (CDCl
2
1
3
,
due to the electronic effect of the methyl groups, while in the
metal complexes, the chemical shift of corresponding H
increases, which can be attributed to the electron-withdrawing
metal ions.
4
00 MHz): 9.172 (s, 8H), 7.937-7.945 (d, 4H), 7.865-7.878
d, 4H), 7.519-7.542 (m, 4H).
(
Copper(II) meso-5,10,15,20-tetra(2-thienyl)porphyrin
compound 5, CuTTP): Bright purple solid, yield 86 %, m.p.
(
-1
The UV-visible absorption spectra of porphyrin derivatives
>
300 °C. IR (KBr, νmax, cm ): 3096, 2921, 2852, 1589, 1426,
351, 1323, 1224, 1170, 1074, 973, 800, 701, 454.
3
in CHCl solution are showed in Figs. 1 and 2. Owing to similar
1
structures, conjugated macrocyclic system of porphyrin ring,
porphyrin derivatives exhibit the strong absorption peaks
located in the range of 400-440 and 500-600 nm which are
Cobalt(II) meso-5,10,15,20-tetra(2-thienyl)porphyrin
(
compound 6, CoTTP): Bright purple solid, yield 80.5 %,
-1
m.p. > 300 °C. IR (KBr, νmax, cm ): 3096, 2921, 2852, 1649,
1
*
attributed to π → π electron transition. Wherein, Soret-band
461, 1328, 1224, 1169, 1071, 979, 815, 702, 463.
Zinc meso-5,10,15,20-tetra(3-methyl-2-thienyl)porphyrin
is a single peak around 420 nm and weak Q-band includes
four absorption peaks between 450 and 600 nm. The values
of the absorption coefficient of Soret-band are about 10 to 20
times of Q-band. Q-band and Soret-band are attributed to the
[
compound 7, ZnT(3-M)TP]:A mixture of compound 3 (0.208
g, 0.3 mmol) and Zn(OAc) (0.1 g, 0.45 mmol) in CHCl (20
mL) and CH OH (8 mL) was refluxed for 2 h.After cooling to
2
3
3
*
*
a
g g
1u(p) → e (p ) energy level transition and a2u(p) → e (p )
room temperature, the mixture was filtered and washed with
water. After drying for 24 h under vacuum, the crude product
was purified by the silica gel column chromatography (petro-
leum ether: ethyl acetate = 5:1), then 0.19 g desired purple
compound 7 was obtained (yield 83.7 %, m.p. > 300 °C). IR
11
energy level transition of the porphin ring, respectively .
1.0
H TTP
2
-1
ZnTTP
CuTTP
CoTTP
(
KBr, νmax, cm ): 3095, 2920, 2852, 1653, 1515, 1458, 1378,
1
329, 1063, 980, 818, 792, 702, 620, 464. H NMR (CDCl
1
3
,
0.8
4
00 MHz): 9.031 (s, 8H), 7.732-7.745 (d, 4H), 7.347-7.357
d, 4H), 2.131-2.224 (m, 12H).
(
0.6
Copper(II) meso-5,10,15,20-tetra(3-methyl-2-thienyl)-
porphyrin [compound 8, CuT(3-M)TP]: Bright purple solid,
-1
0.4
0.2
0
yield 82.4 %, m.p. > 300 °C. IR (KBr, νmax, cm ): 3099, 2917,
2
7
853, 1646, 1520, 1450, 1370, 1335, 1067, 984, 821, 794,
08, 618, 468.
Cobalt(II) meso-5,10,15,20-tetra(3-methyl-2-thienyl)-
porphyrin [compound 9, CoT(3-M)TP]: Bright purple solid,
-1
yield 86.7 %, m.p. > 300 °C. IR (KBr, νmax, cm ): 3097, 2920,
400
500
600
2
4
852, 1646, 1568, 1433, 1340, 1070, 991, 822, 794, 710, 618,
67.
Wavelength (nm)
Fig. 1. UV-visible spectra of H TTP and its metal complexes
2

Vol. 27, No. 2 (2015)
Synthesis and Optical/Electrochemical Properties of meso-5,10,15,20-Tetrathienyl Substituted Porphyrins 619
1.0
0.8
0.6
0.4
0.2
0
M),CuTTP, CuT(3-M)TP, CoTTP and CoT(3-M)TP are blue-
shifted in contrast to the corresponding ligands in the order of
Zn < Cu < Co, which indicates that the blue-shifted Q-band
absorption peaks increase with the increase of metal atomic
number.
H T(3-M)TP
2
ZnT(3-M)TP
CuT(3-M)TP
CoT(3-M)TP
3
The fluorescent studies are performed in CHCl with
scanning wavelength between 300 and 700 nm (Fig. 3) and
the corresponding data are collected in Table-2. The Stokes
shifts decrease when metal complexes are formed.Along with
2
+
2 2
the complexation of H TTP and H T(3-M)TP with Zn ,
the fluorescence emission improves greatly, whereas the
fluorescence quenching effect arises when the complexation
2
+
2+
of H
2 2
TTP and H T(3-M)TP with Cu and Co occur. This is
2+
possibly due to the electron-deficiency in 3d orbit of Cu and
2
+13
2
Co . Fig. 4 shows the photoluminescence spectra of H TTP,
400
500
600
H T(3-M)TP, ZnTTP and ZnT(3-M)TP with excitation
2
Wavelength (nm)
wavelength at 426 nm. It is shown that the maximum emission
Fig. 2. UV-visible spectra of H T(3-M)TP and its metal complexes
2
2 2
wavelength of H TTP, H T(3-M)TP, ZnTTP and ZnT(3-M)TP
is at 724, 727, 666 and 654 nm, respectively. Similarly to the
fluorescence, the photoluminescence of ZnTTP and ZnT(3-
M)TP are blue-shited in contrast to their ligands, while no
photoluminescence occurs for compound CuTTP, CuT(3-
M)TP, CoTTP and CoT(3-M)TP. The photoluminescence
intensity of H TTP and H T(3-M)TP are greater than that of
Fig. 1 shows the UV-visible spectra of H
complexes in CHCl and Fig. 2 shows the UV-visible spectra
of H T(3-M)TP and its metal complexes in CHCl . In the
visible region, both H TTP and H T(3-M)TP exhibit the strong
absorption peaks (Soret-band) and four weak absorption peaks
Q-band). When the metal complexes formed, the Q-band
absorption peaks were reduced to one peak. The main reason is
that compound H TTP and H T(3-M)TP are D2h point groups,
2
TTP and its metal
3
2
3
2
2
2
2
(
ZnTTP and ZnT(3-M)TP, respectively.
2
2
1
00
80
60
which determine the Q-band is consist of four absorption peaks.
When the metal ion was embedded into the porphyrin ring,
the metal ion occupied the center of the porphyrin ring. Along
with the four N atoms of porphyrin ring are coordinated with
the metal ion, the symmetry of the metal complex and the
degeneracy of molecular orbital increase, while the energy
levels and the degree of the molecular orbital splitting decrease.
H TTP
H T(3-M)TP
ZnT(3-M)TP
ZnTTP
2
2
4
0
0
0
12
The porphyrin metal complexes are D4h point groups , which
usually lead to the number and intensity of the Q-band
absorption peaks decrease in UV-visible spectra. This is also
the typical characteristic of the formation of metalloporphyrin
complexes.
2
450
500
550
600
650
700
The UV-visible spectra absorption data of the synthesized
porphyrin and metalloporphyrin complexes are shown in
Table-1. It indicates that the metalloporphyrin complexes only
have one Q-band absorption peak and the Soret-band absor-
ption peaks of ZnTTP and ZnT(3-M) are red-shifted than
Wavelength (nm)
TTP, H T(3-M)TP, ZnTTP and ZnT(3-
Fig. 3. Fluorescent spectra of H
2
2
M)TP
1400000
1200000
1000000
H T(3-M)TP
2
2 2
H TTP and H T(3-M)TP. In contrast, compound CuTTP,
ZnT(3-M)TP
H TTP
ZnTTP
CoTTP, CuT(3-M)TP and CoT(3-M)TP are blue-shifted. The
Q-band absorption peaks of metalloporphyrin ZnTTP, ZnT(3-
2
8
6
4
2
00000
00000
00000
00000
0
TABLE-1
UV-VISIBLE SPECTRAL DATA OF
PORPHYRIN AND METALLOPORPHYRIN
Compound
Soret band (nm)
Q band (nm)
H TTP
2
426
427
420
417
426
427
421
416
463
466
522
560
554
546
538
557
553
545
535
596
595
ZnTTP
CuTTP
CoTTP
H T(3-M)TP
2
521
400 450 500 550 600 650 700 750 800 850
Wavelength (nm)
ZnT(3-M)TP
CuT(3-M)TP
CoT(3-M)TP
Fig. 4. Photoluminescence spectra of H
2 2
TTP, H T(3-M)TP, ZnTTP and
ZnT(3-M)TP

620 Zhou et al.
Asian J. Chem.
TABLE-2
FLUORESCENT SPECTRAL DATA OF
PORPHYRIN AND METALLOPORPHYRIN
TABLE-3
ELECTROCHEMICAL PROPERTIES OF H TTP,
H T(3-M)TP AND THEIR METAL COMPLEXES
2
2
ox
red
E
Ip
EHOMO
E
Ea
ELUMO
Eg
Compounds
Ex(nm)
560
Em(nm) Stokes shift (nm)
Compounds
(
V)
(eV) ( eV ) (V)
5.06 -5.06 -1.25
5.11 -5.11 -1.28
5.19 -5.19 -1.27
5.20 -5.20 -1.28
5.05 -5.05 -1.28
5.08 -5.08 -1.30
5.14 -5.14 -1.26
5.16 -5.16 -1.28
(eV ) ( eV ) ( eV )
H TTP
2
667
659
107
102
H TTP
2
0.66
0.71
0.79
0.80
3.15
3.12
3.13
3.12
3.12
3.10
3.14
3.12
-3.15
-3.12
-3.13
-3.12
-3.12
-3.10
-3.14
-3.12
1.91
1.99
2.06
2.08
1.93
1.98
2.00
2.04
H T(3-M)TP M)TP
2
557
ZnTTP
CuTTP
CoTTP
ZnTTP
554
610
56
ZnT(3-M)TP
553
603, 645
50, 92
H2T(3-M)TP 0.65
ZnT(3-M)TP 0.68
The electrochemical properties of all the synthesized
compounds are obtained from cyclic voltammograms (Figs. 5
and 6). The onset of the oxidation and reduction are shown in
CuT(3-M)TP 0.74
CoT(3-M)TP 0.76
Table-3. The ionization potential (I
p a
), electronic affinity (E ),
2
thienyl)porphyrin (H T(3-M)TP) and their cobalt, copper and
HOMO energy level (EHOMO) and LUMO energy level (ELUMO)
OX
14
zinc complexes were successfully synthesized. The optical
properties, UV-visible absorption spectra, fluorescence spectra
and photoluminescence spectra of them were investigated and
p
are calculated using the equation : I = -EHOMO, EHOMO = -[E
Red
+
E
4.4] eV, E
a g
= ELUMO, ELUMO = -[E + 4.4] eV, E = EHOMO -
LUMO. Table-3 shows that the ELUMO change slightly than that
their electrochemical properties such as band-gaps (E
g
),
g
of EHOMO and meanwhile the electrochemical band-gaps (E )
ionization potential (I ), electronic affinity (E ), HOMO energy
p
a
become larger when the complexation of H TTP and H
2
2
T(3-
level (EHOMO) and LUMO energy level (ELUMO) were also
recorded. The Soret-band absorption peak of the synthesized
zinc porphyrin complex was red-shifted, in contrast, copper(II)
and cobalt(II) porphyrin complexes were blue-shifted. With
the increases of the metal atomic number, the Q-band
absorption peak blue-shift increases in the order Zn < Cu <
Co. When the synthesized two kinds of porphyrin compounds
M)TP with metal ions occur.
200
150
100
H TTP
2
ZnTTP
CuTTP
CoTTP
2+
50
are coordinated with Zn , the fluorescence intensity enhances.
The electrochemical properties indicate that ELUMO has smaller
change than EHOMO, meanwhile the electrochemical band-gaps
0
(
g
E ) became larger when metal complexes were formed.
-50
ACKNOWLEDGEMENTS
-100
The financial support from the National Nature Science
Foundation of China (21176193) is gratefully acknowledged.
-1.5
-1.0
-0.5
0
0.5
1.0
1.5
Potential (V)
Fig. 5. Cyclic voltamograms of H TTP and its metal complexes
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H T(3-M)TP
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1.5
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2
Fig. 6. Cyclic voltamograms of H T(3-M)TP and its metal complexes
1
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Conclusion
1
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Two kinds of meso-5,10,15,20-tetrathienyl substituted
porphyrin compounds, meso-5,10,15,20-tetra(2-thienyl)-
2
porphyrin (H TTP), meso-5,10,15,20-tetra(3-methyl-2-