Inorganic Chemistry Communications 13 (2010) 236–239

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Inorganic Chemistry Communications

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Synthesis and properties of iron(II) tetra(1,4-dithiin)porphyrazine bearing

peripheral long-chain alkyl group of active end-bromine
Junfeng Tang, Lianqing Chen *, Jie Sun, Kangle Lv, Kejian Deng *
Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, Hubei Province,
South-Central University for Nationalities, Wuhan 430074, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The novel tetra-(1,4-dithiin) metal-free (H2Pz) and metalloporphyrazines (MPz, M = Mg, Fe) bearing
Received 17 July 2009 peripheral tetrapropyl-bromine derived from 2,3-dicyano-5-propyl-bromine-1,4-dithiin, were synthe-
Accepted 23 November 2009 sized in a multi-step reaction sequence. These complexes were characterized by 1H NMR, IR, UV–vis,
Available online 27 November 2009
GC–MS, XPS and elemental analysis and their UV–vis spectra were discussed in detail. The iron(II)
tetra-(1,4dithiin)porphyrazine bearing peripheral tetrapropyl-bromine was supported on an Amberlite
Keywords: CG-400 resin to form a biomimetic catalyst, the ability of which for activating O2 and H2O2 was estimated
Sulfur-containing porphyrazine iron(II)
from the degradation of Rhodamine B (RhB) under visible light irradiation (k P 420 nm). More than 70%
Synthesis
Activating molecular oxygen
of the RhB was degraded by O2 in air for 24 h in the solution of pH 9.18 and by H2O2 only for 12 h in the
Biomimetic catalyst solution of pH 3.0.
Photodegradation Ó 2009 Elsevier B.V. All rights reserved.

Metalloporphyrazines (MPzs) with an extended delocalized 18
p-electron conjugated macrocyclic system, which exhibit high
thermal stability and unique photoelectron performance, are usu-
ally used as biomimetic photocatalysts [1,2]. Several biomimetic
catalysts synthesized modeling on the cytochrome P-450 have
been described extensively in oxidative degradation of persistent
organic pollutants due to their capabilities for activating small
molecular oxidants O2 and H2O2 [3–5]. The processes which mimic
the oxidation characteristics of iron-containing oxygenase en-
zymes are interesting because of their ‘‘clean” and ‘‘green” charac-
teristics [3–9]. Among these biomimetic catalysts, iron(II)
bipyridine (FeBR) showed a excellent catalytic activity. But the
FeBR itself could not activate dioxygen to produce reactive oxidiz-
ing species, it displayed the excellent catalytic activity only when
supported on cationic ion-exchanged resin [5]. Its mechanism to
activate dioxygen was not very clear so as to further develop FeBR
to occur difficulty. The iron(II) tetra(1,4-dithiin)porphyrazine (de-
noted as FePz(dtn)4) and its derivatives were investigated to be
good photocatalyst to activate dioxygen when it was straightly dis-
solved in water [10] or supported on an anion exchange resin
(Amberlite CG-400) [11]. Oxidative degradation of persistent or-
ganic pollutants using the photocatalyst like FePz(dtn)4 to activate
green oxidants, especially molecular oxygen under visible light
irradiation is still a challenge in treating waste water [12]. A deci-
sive disadvantage of the FePz(dtn)4 is their solubility in water or
organic solvents [13,14]. The complex must disperse in water by
* Corresponding author. Tel.: +86 27 67843930; fax: +86 27 67842752.
E-mail address: dengkj@scuec.edu.cn (K. Deng).
means of the hydrophilic property of the anion exchange resin.
The solubility of these compounds could be improved by introduc-
ing bulky or long chain groups, e.g. alkyl, alkoxy, quaternized
ammonium, sulfonamide, polyalcohol, etc. into the peripheral sites
of the porphyrazines/phthalocyanines [15,16]. Improvement of
lipophilic property of the complexes enables them easy to load
onto the resin carrier and to close to the substrates.
In this work, three new tetra(1,4-dithiin)porphyrazine bearing
peripheral tetrapropyl-bromine were synthesized and fully charac-
terized, and their general route for the synthesis of new porphyra-
zines was shown in Scheme 1. The experiment results show that
the lipophilic capability of porphyrazine has been improved. Com-
plex 8 can be not only used as an intermediate to synthesize much
more derivatives of sulfur-containing porphyrazine with some
vagarious structures; but also exhibits good catalytic performance
when it was supported on the Amberlite CG-400 anion exchanged
resin as a biomimetic photocatalyst.
The synthesis of these complexes, along with the chemical and
physical methods employed for its characterization, is described in
Supplementary material.
GC–MS spectrum of the compound 3 exhibited a molecular ion
peak at m/z = 310 [M+1]+, which supports the proposed formula-
tion. The intermediate 2,3-dicyano-5-propyl-bromine-1,4-dithiin
5 was prepared according to the literature procedure [17]. 1H
NMR spectrum of 5 showed the expected signals such as –S–CH,
–S–CH2–, –Br–CH2–, –CH2– protons at d = 4.19, 3.36, 3.2 and
1.95 ppm, respectively. The IR (KBr, cm1) spectrum of 5, 2925,
2852 for C–H, 2208 for C„N, 1635, 1504 and 1379 for C@C,
1282 and 1171 for C–C, 1046 and 850 for C–S, 499 for C–Br,

1387-7003/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2009.11.020
 J. Tang et al. / Inorganic Chemistry Communications 13 (2010) 236–239 237

Ice-bath Br NaS CN DME

Br + Br2 Br
+
CH2Cl2
NaS CN 70
Br
1 2 3 4
Br Br
S S
N
S CN S S
Br N N CF3COOH
(n-BuO)2Mg, PhCl
N Mg N N2
CH2Cl2 N N
S CN
S S
N
S S
5 Br 6 Br

Br Br Br Br

S S S S
N N
S S S S
NH N PhCl, DMF N N
N N N Fe N
FeSO4, N2
N HN N N
S S S S
N N
S S S S
Br Br Br Br
7 8

Scheme 1. Synthesis of the metal-free porphyrazine and metallo-porphyrazines.

confirms the structure of 5. GC–MS spectrum of 5 exhibited a
molecular ion peak at m/z = 290 [M+1]+, conforming the proposed
formulation.
Porphyrazinatomagnesium 6 was obtained by the template
reaction [18] of compound 5 with magnesium butoxide in dry n-
butanol under nitrogen at reflux temperature. Typically, compound
5 has poor solubility in n-butanol, but good solubility in chloroben-
zene, so the compound 5 dissolved in chlorobenzene was added
dropwise to the refluxing reaction mixture to improve the yield
from 5.5% to 62.5%. In the 1H NMR spectrum of complex 6, the sig-
nals related to –S–CH–, –SCH2–, –BrCH2–, and –CH2– groups were
observed at d = 2.89, 3.71, 3.0 and 2.11, 1.89 ppm, respectively. In
the IR spectrum of compound 6, after conversion of dinitrile deriv-
ative 5 to porphyrazinatomagnesium 6, the disappearance of sharp
C„N stretching vibrations at 2208 cm1 and appearance of C@N
stretching vibrations at 1640 cm1 belonging to the synthesized
compound. Porphyrazinatomagnesium 6 displays the molecular
ion peak at m/z = 1182.13 [M+1]+. In the 1H NMR spectrum of 7, in-
ner core NH protons appear as a deuterium exchangeable broad
spectrum with well resolved split Q-band at 707 and 625 nm as a
consequence of the change in the symmetry of metal-free porphyr-
azine core from D4h to D2h [22]. It is observed a slight red-shift of
the soret band in metal-free compound 7 and this behavior is typ-
ical for substituted porphyrazines.
The IR spectrum of compound 8 very resembles that of the pre-
cursor compound 7 except NH stretching vibration. Porphyrazina-
tozinc complex 8 displays the expected molecular ion peak at m/
z = 1213.74 [M+1]+, which also supports the structure of the target
1.4
1.2
1.0
Absorbance

chemical shift at = 3.36 ppm as a consequence of the 18 p-elec-

tron systems of the planar structure [19,20]. The mass spectrum 0.8
data of 7 contained a strong peak at m/z = 1159.91 [M+1]+ for the
parent ion, which can be attributed to the formation of the me- 0.6
tal-free porphyrazine.
The best indications for porphyrazine systems are given by their
UV–vis spectra in chloroform solution (105 M) at room tempera- 0.4

ture (Fig. 1). The absorption spectra of 6 and 7 show the same typ-
ical B and Q bands of symmetrical substituted porphyrazine. The 0.2
single band at 672 nm of 6, is characteristic of tetrapyrrolic macro-
cycle with D4h symmetry and is related to p?p* transition [1]. The
0.0
broad absorption band around 540 nm is assigned to the n?p* 300 400 500 600 700 800
transitions of the nonbonding electrons of the peripheral sulfur
Wavelength/nm
atoms and the macrocyclic p system [21,22]. Demetallation to pro-
duce the corresponding metal-free derivative results in the UV–vis Fig. 1. UV–vis spectra of 6 (solid line) and 7 (dashed) in the chloroform solution.
238 J. Tang et al. / Inorganic Chemistry Communications 13 (2010) 236–239

compound. We have inspected the reaction with UV–vis spectrum 1.0

along with the reaction time (Fig. 2). Raw solution
The ability of complex 8 for activating O2 and H2O2 was esti-
mated from the degradation of Rhodamine B (RhB) in water 0.8
COOH
under visible light irradiation (k P 420 nm). Photocatalytic degra- 0h

Absorbance
dation of RhB in the presence of complex 8 /resin was performed 0.6 6h
at pH 9.18 through aerating with O2 in air, and the UV–vis
absorption spectra of the RhB at different intervals during 24 h Et2N o NEt2 Cl 12h
irradiation are shown in Fig. 3. It is observed that the character- 0.4
15h
istic kmax of RhB at 555 nm decreased continuously with some
hypsochromic shifts, and that absorbance for degraded products 24h
in the UV region slightly increased during the irradiation process. 0.2
The RhB in the solution has been effectively degraded by about
74% after irradiation for 24 h. The results show that the chro-
0.0
mophores of RhB, including the substituent groups and the mol- 200 300 400 500 600
ecule frame, were effectively cleaved. The hypsochromic shifts Wavelength / nm
of the maximum absorption of RhB are attributed to the de-eth-
ylening [23]. Fig. 3. The dynamic process of photodegradation for the RhB with an original
concentration of 1  105 mol/L in an aerated suspension with air at pH 9.18
Control experiments on the photodegradation of RhB are shown
characterized by UV–vis spectral changes of RhB sampled during 24 h visible
in Fig. 4. No significant change in the degradation of RhB was ob- irradiation in the presence of Fe(II) porphyrazine 8 supported on resin with loading
served in the following reaction conditions: (a) in the dark (curve amount of 6.0‰.
a); (b) suspension aerated with N2 (curve b); (c) without catalyst
(curve c). However, in the presence of the resin-supported-catalyst,
molecular oxygen and visible light irradiation (k P 420 nm), more
than 45% of RhB were degraded as curve d. The limited degradation
of RhB in the absence of catalyst may be attributed to self-photo-
1.0
sensitized oxygenation of RhB through singlet oxygen, while the
small amount of RhB degraded on bubbling with N2 could be due a
to the oxygen remaining in the system. Thus, it can be concluded
that the degradation of RhB is a photocatalytic oxygenation process 0.8
(curve d). The RhB molecules were strongly absorbed near the cat- f
f

alyst in alkaline solution of pH 9.18 under the visible region, which b

Ct / C 0

was responsible for their degradation [11]. The process may in- f

c
volve an activating process through electron transfer from the cen- 0.6
tral iron(II) ion to the molecular oxygen coordinated with Fe(II)
porphyrazine 8 to form an reactive oxidizing species, such as a
O 
2 or/and OH radical that could oxygenate RhB and cleave it effec-
0.4
tively [24].
If H2O2 was used to replace O2 as an oxidant (the concentration
of H2O2 0.0167 mol/L), in the acid solution (pH 3.0) the catalyst 8 e d
activity increase a time more than that of O2 as oxidant in alkaline 0.2
solution (pH 9.18) as curve e in Fig. 4. More than 70% of the RhB 0 5 10 15 20 25
was degraded by air for 24 h in the solution of pH 9.18 and by Time / h
Fig. 4. Control experiments on the photodegradation of RhB: (a) RhB/Fe(II)
porphyrazine 8/resin/air/dark at pH 9.18; (b) RhB/ Fe(II) porphyrazine 8/resin/N2/
0.5 light at pH 9.18; (c) RhB/resin/air/light (without catalyst) at pH 9.18; (d) RhB/Fe(II)
16h porphyrazine 8/resin/air /light at pH 9.18; (e) RhB/Fe(II) porphyrazine 8/resin/H2O2/
14h light system at pH 3.0; (f) RhB/H2O2/light system (without catalyst) at pH 3.0.

0.4
12h
H2O2 only for 12 h in the solution of pH 3.0. While the RhB in same
Absorbance

0.3 concentration of H2O2 and the absence of catalyst was limitedly

0h degraded as curve f. The reason may be that H2O2 is a single oxygen
donor to be able to oxygenate the central metal of the catalyst 8 to
0.2 high oxidation state [25] and the proton in acid solution is also
helpful for generation of high oxidation state Pz+FeIV@O radicals
[26] so that the reaction rate rapidly increase. The further research
0.1 is being done.

Acknowledgments
0.0
400 450 500 550 600 650 700 750 800
This work was financially supported by National Natural Sci-
Wavelength / nm
ence Foundation of China (Nos. 20577070, 20702064, 20807057)
Fig. 2. Some changes of Q band from metal-free porphyrazine 7 (1  105 mol/L in and Science Project of Chinese National Affairs Committee
the chloroform solution) to metallated porphyrazine 8 along with the reaction time. (MZZ04003).
 J. Tang et al. / Inorganic Chemistry Communications 13 (2010) 236–239
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.inoche.2009.11.020.
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