Tris(N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamato-S,S′)cobalt(III) for anion sensing and preparation of cobalt-iron sulfide nanoparticles: A new photocatalyst for the degradation of dyes

Article abstract of DOI:10.1080/10426507.2018.1539720

Tris(N-(pyrrol-2-ylmethyl)-N-butyldithiocarbamato-S,S′)cobalt(III) (1) and tris(N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamato-S,S′)cobalt(III) (2) have been synthesized and characterized by elemental analysis and spectroscopy (IR, UV-vis and NMR). T

Full text of DOI:10.1080/10426507.2018.1539720

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Tris(N-methylferrocenyl-N-(2-
phenylethyl)dithiocarbamato-S,S′)cobalt(III) for
anion sensing and preparation of cobalt-iron
sulfide nanoparticles: A new photocatalyst for the
degradation of dyes
Subbiah Thirumaran & Govindasamy Gurumoorthy
To cite this article: Subbiah Thirumaran & Govindasamy Gurumoorthy (2018): Tris(N-
methylferrocenyl-N-(2-phenylethyl)dithiocarbamato-S,S′)cobalt(III) for anion sensing and
preparation of cobalt-iron sulfide nanoparticles: A new photocatalyst for the degradation of dyes,
Phosphorus, Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2018.1539720
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1539720
0
Tris(N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamato-S,S )cobalt(III) for
anion sensing and preparation of cobalt-iron sulfide nanoparticles: A new
photocatalyst for the degradation of dyes
Subbiah Thirumaran and Govindasamy Gurumoorthy
Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram, Tamil Nadu, India
ABSTRACT
ARTICLE HISTORY
Received 26 July 2018
Accepted 19 October 2018
0
Tris(N-(pyrrol-2-ylmethyl)-N-butyldithiocarbamato-S,S )cobalt(III) (1) and tris(N-methylferrocenyl-N-
0
(
2-phenylethyl)dithiocarbamato-S,S )cobalt(III) (2) have been synthesized and characterized by
1
elemental analysis and spectroscopy (IR, UV-vis and NMR). The elemental analysis and IR, H and
1
3
KEYWORDS
C NMR spectra are consistent with the formation of the cobalt(III) complexes with dithiocarba-
Anion sensing; cobalt(III)
dithiocarbamate; cobalt-iron
sulfide; nanoparticles; single
source precursors
mate ligands. The anion binding properties of 1 and 2 based on host-guest interaction have been
examined with the use of cyclic voltammetry.This study showed that both complexes preferred to
bind with I compared to other halides. 2 has been used as precursors for the preparation of
-
cobalt-iron sulfide nanoparticles. TEM image of cobalt-iron sulfide nanoparticles showed that the
particles are spherical. The elemental compositions of the nanoparticles were confirmed by energy
dispersive X-ray spectroscopy. IR spectral studies on nanoparticles confirm the presence of cap-
ping agent (triethylenetetramine). The nanoparticles were explored as photocatalysts to study the
degradation of dyes using methylene blue and rhodamine-B in aqueous solution under UV irradi-
ation. The cobalt-iron sulfide works as an efficient photocatalyst for degradation of rhodamine-B.
GRAPHICAL ABSTRACT
Introduction
[13,14]
nanoparticles.
These nanoparticles have been used for the
A wide range of metal-dithiocarbamate complexes is known photocatalytic degradation of various organic pollutants such
[
15,16]
with examples finding use in applications as diverse as indus- as dyes and p-nitrophenol.
The photocatalytic activity of
[1–7]
try, agriculture, medicine and material science.
fide nanoparticles have shown vital applications in many fields and size of the nanoparticles.
Metal sul- the metal sulfide nanoparticles depends on the morphology
[17]
Furthermore, transition metal
such as IR detectors, photocapacitors for energy conversion dithiocarbamates containing redox active ferrocene moiety are
[6]
[
7]
[8]
[9]
[18,19]
and storage, sensors,[ photonic materials and advanced used as sensors for anions.
Particularly, cobalt(III) dithio-
In recent years, transition metal carbamate complexes have been used as catalysts for the syn-
dithiocarbamate complexes have received a great deal of atten- thesis of b-enaminoesters and b-enaminones from 1,3-
10]
optoelectronic devices.
[20]
[21,22]
tion because of their importance as single source precursors diketones and b- ketoesters,
sensor for ions
and single
[11,12]
for the preparation of metal sulfide nanoparticles.
bound organic moieties in dithiocarbamate ligands in metal ticles.
complexes affect the morphology and size of the metal sulfide complexes for the sensing of anions and preparation of cobalt
The N- source precursors for the preparation of metal sulfide nanopar-
[23]
Our aim is to prepare cobalt(III) dithiocarbamate
CONTACT Subbiah Thirumaran
sthirumaran@yahoo.com
Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002,
Tamil Nadu, India.
Supplemental data for this article can be accessed on the publisher’s website at https://doi.org/10.1080/10426507.2018.1539720
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
ß 2018 Taylor & Francis Group, LLC

2
S. THIRUMARAN AND G. GURUMOORTHY
Scheme 1. Preparation of the complexes 1 and 2.
sulfide and cobalt-iron sulfide nanoparticles. In this paper we IR spectral studies
report, synthesis and characterization of tris(N-(pyrrol-2-
The IR spectra of the metal dithiocarbamate complexes are
used to find the coordination mode (monodentate or biden-
0
ylmethyl)-N-butyldithiocarbamato-S,S )cobalt(III)
(1)
and
tris(N-methylferrocenyl-N-(2-phenylethyl)dithiocarbamato-
[24]
tate) of the dithiocarbamate ligands.
In the case of a
0
S,S )cobalt(III) (2) and their utilization for anion sensing and
in addition, preparation of cobalt-iron sulfide nanoparticles
from complex 2 and photocatalytic behavior of as-prepared
nanoparticles for dye degradation are presented.
bidentate coordinating mode, a solitary band is observed in
ꢀ1
the region of 950–1050 cm while the splitting of this band
ꢀ1
within a narrow range of 20 cm is due to the monoden-
tate coordination of dithiocarbamate ligand. Only one band
associated with the C-S stretching is observed around 1027
ꢀ
1
cm for 1 and 2 in the IR spectra confirming the bidentate
Results and discussion
coordination mode of the ligands. The spectral region from
ꢀ
1
1
450-1500 cm
is associated with the ꢀC-N (thioureide)
Complexes 1 and 2 were prepared according to the synthetic
procedure shown in Scheme 1. Butylamine and 2-phenylethyl-
amine were condensed with pyrrole-2-carboxaldehyde and ferro-
cenecarbaldehyde, respectively, to form the imines. The imines
vibrational mode. For complexes 1 and 2, the (ꢀC-N) (thio-
ꢀ
1
ureide) were found around 1485 cm , indicating the partial
double bond character. The vN-H value exhibited by 1
ꢀ
1
(
3380 cm ) indicates the non-involvement of pyrrole nitro-
were reduced with NaBH to yield the secondary amines. 1 and
4
gen in the coordination.
2
were prepared from the secondary amine by reaction with CS2
and CoCl . The complexes are quite stable at ambient condi-
2
tions. They are soluble in chloroform, dichloromethane and NMR spectral studies
acetonitrile and insoluble in ethanol and methanol.
1
H NMR spectral studies
The protons of methylene group attached to pyrrole group
in complex 1 appear around 4.75 ppm. The remaining three
signals in the aliphatic region are due to the butyl group;
IR, UV-vis and NMR ( H and C) spectra of complexes 1 and that shifted to lower field being nitrogen bound. NH pro-
are shown in Figures S 1 to S 8 (Supplemental Materials). tons of pyrrole rings are observed at 9.04 ppm. The
Spectral studies
1
13
2

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
methylene protons of ferrocenyl methyl, NCH protons of a single step and are electrochemically independent of one
2
[
18]
ꢀ
ꢀ
ꢀ
ꢀ
NCH CH C H and ferrocene ring protons are appeared in another.
The addition of F , Cl , Br and I anions to
2
2
6
5
the region 3.65–4.80 ppm for complex 2. The aromatic electrochemical solution of the complex 2 resulted in signifi-
ꢀ
proton signals of both complexes are appeared in the region cant cathodic shifts of ferrocene redox couple. I induced
6
.15–7.30 ppm.
larger magnitudes of cathodic shift in the ferrocene redox
ꢀ
ꢀ
ꢀ
couple compared to F , Cl and Br (Table 1). This sug-
ꢀ
gests a preferential binding interaction with the I anion.
1
3
C NMR spectral studies
No detectable shifts were observed for Co(III) dithiocarba-
For complex 1, the signals for methylene carbon attached to
pyrrole and NCH (butyl) carbons are observed at 48.1 and
[28]
mate imidazolinium cryptand receptor.
Tris(N-furfuryl-
2
N-methylferrocenyldithiocarbamato-S,S)cobalt(III) preferred
4
4.7 ppm, respectively. The other signals that appeared in
ꢀ
ꢀ
ꢀ
to bind with Br compared to those of benzoate, F and I
ions.
the aliphatic region of 1 are assigned to the remaining car-
bons of methylene and methyl of butyl group. In the case of
complex 2, the signals observed at 33.4, 47.9 and 49.2 ppm
are due to methylene carbon of N-CH -CH -C H , ferro-
[22]
These studies indicates that anion sensing property
of complexes depends on N-bound organic moiety of dithio-
carbamate ligand.
2
2
6
5
cenyl methyl group and N-CH -CH -C H , respectively.
2
2
6
5
Ferrocene ring carbons resonate in the region 68.5-77.2. The Characterization of metal sulfide nanoparticles
1
3
important C NMR chemical shift value of the thioureide
The morphological characterization of cobalt-iron sulfide
nanoparticles was carried out using TEM and is shown in
Figure 2. TEM image demonstrated that cobalt-iron sulfide
are perfect spherical and quasispherical in shape and the
particles diameter are in the range 11–35 nm. Synthesis and
characterization of cobalt iron sulfide nanoparticles from tris(N-
1
3
carbon (N CS ) was observed at 205.6 and 205.0 ppm for 1
2
and 2, respectively due to the partial double bond character
of N-CS bond in the dithiocarbamate ligands.
2
Electronic spectral studies
furfuryl-N-methylferrocenyldithiocarbamato-S,S)cobalt(III) were
UV-vis spectra of metal-dithiocarbamate complexes usually
show three absorption bands in the ultraviolet region due to
[22]
reported.
This nanoparticles are cuboid. Hence, the shape of
nanoparticles are influenced by the N-bound organic moiety of
dithiocarbamate ligand.
ꢁ
ꢁ
p-p transition of NCS and SCS moiety and n-p transition
(
i.e. transfer of a electron of the lone pair on the S to an
To confirm the chemical composition of the product,
cobalt-iron sulfide are analyzed using Energy dispersive X-
ray spectroscopy (EDS). Energy dispersive X-ray spectrum
of cobalt-iron sulfide nanoparticles are displayed in Figure S 9
and the EDS data shows that the ratio of Co:Fe:S in cobalt
iron sulfide is 1:1.7:2.5. This confirms the formation of cobalt-
iron sulfide
The optical properties of cobalt-iron sulfide were studied
by the UV-vis absorption and photoluminescence (PL) spec-
troscopic techniques and are shown in Figures S 10 and
S 11. The room temperature absorption and emission spec-
tra were recorded by dispersing the samples in ethanol.
[
25]
antibonding p-orbital).
In the present study, these three
bands are observed around 250, 275 and 325 nm. The band
which appeared around 400 nm may be due to either metal-
!
ligand or ligand! metal charge transfer. Complexes 1
and 2 show two bands in the visible region (488 and 642
nm for 1 and 472 and 632 nm for 2) due to d-d transitions.
The absorption pattern suggests an octahedral coordination
[
26]
around Co(III).
Preliminary anion binding studies
The anion sensing studies of complexes 1 and 2 with bio- Optical absorption spectra of cobalt sulfide exhibit a band at
ꢀ
ꢀ
ꢀ
ꢀ
logically important anions like F , Cl , Br and I were 264 nm, which is blue shifted from the absorption edge of
performed using cyclic voltammetry and cyclic voltammo- the bulk cobalt sulfide[29] and iron sulfide.
[30]
The increase
grams are displayed in Figure 1. Both the complexes were in band gap energy of cobalt-iron sulfide nanoparticles indi-
examined for their anion sensing ability by cyclic voltamme- cates the quantum confinement effect due to the decrease in
ꢀ
4
try in 1 ꢂ 10 M CH CN solution containing 0.01 M of size. The PL spectrum of cobalt-iron sulfide shows a broad
3
tetrabutylammonium
fluoroborate
as
supporting peak at 422 nm. This is due to the radiative transition of
electrolyte.The cyclic voltammogram of complex 1 shows electrons from shallow trap states near the conduction band
reduction at ꢀ1.1555V. This is one electron reduction and to sulfur vacancies residing near the valence band.
similar reduction was observed in cobalt (III) dithiocarba-
The FT-IR spectrum of cobalt-iron sulfide nanoparticles
[
27]
mate complexes.
Upon the addition of halide ions, com- is shown in Figure S 12. In IR spectrum, the bands in the
ꢀ
1
plex 1 exclusively response to I, with the reduction potential region 2850–2960 cm are assigned to C-H vibrations of
ꢀ
1
of the complex 1 shift from ꢀ1.1555 V to ꢀ1.5568 V (DE = the sample. A broad peak observed around 3400 cm can
ꢀ
ꢀ
ꢀ
0
.4013 V) however, the addition of F , Cl and Br shows be assigned to the N-H stretching mode. These observations
very less change in reduction potential of the complex 1 suggest the presence of capping agent triethylenetetramine.
ꢀ
1
(
0.025–0.063 V). The tris(N-methylferrocenyl-N-(2-phenyle- The absence of bands around 1480 cm and 3060–3150
0
ꢀ1
thyl)dithiocarbamato-S,S )cobalt(III) (2) containing three fer- cm due to C-N (thioureide) and C-H (aromatic) stretch-
rocenyl groups exhibits a single oxidation wave at 0.8816 V ing modes confirm that dithiocarbamate ligands are not pre-
which suggests that three ferrocene moieties are oxidized in sent with the cobalt-iron sulfide.

4
S. THIRUMARAN AND G. GURUMOORTHY
Figure 1. Changes in the cyclic voltammograms of complexes (a) 1 and (b) 2 on the additions of anions.
Photocatalytic activity
Table 1. Electrochemical anion recognition data of complexes 1 and 2.
The photocatalytic activity performance of as-prepared cobalt-
iron sulfide was evaluated by photocatalytic degradation of
methylene blue and rhodamine-B in aqueous solutions. It
should be noted that the experiment in the absence of catalyst TBA Fluoride
exhibited negligible amount of methylene blue and rhodamine-
Complex (1)
Complex (2)
Anions complex
a
b
Epc (V)
DE1/2 (V)
Epc (V)
DE1/2 (V)
Complex
ꢀ1.1555
ꢀ1.0960
ꢀ1.2187
ꢀ1.1307
ꢀ1.5568
_
0.8955
0.9051
1.3115
1.1893
1.4587
_
0.0595
0.0632
0.0248
0.4013
0.0096
0.4160
0.2938
0.5632
TBA Chloride
TBA Bromide
TBA Iodide
a
B photodegradation, indicating that self photolysis of methy-
lene blue and rhodamine-B is negligible under ultraviolet
irradiation. The degradation of methylene blue and rhoda-
mine-B dyes under ultraviolet light irradiation was followed by
shift of Co(III) /Co(II) reduction potential produced by the anions.
b
shift of Fc/Fcþ oxidation potential produced by the anions.
spectrophotometric monitoring. The experimental results are dyes in presence of catalyst (cobalt-iron sulfide) with UV light
expressed by the change in relative concentration of dyes with irradiation. After irradiation of 180 min, the spectra suggest
irradiation time and are shown in Figure 3. This shows the the 95% and 97% of degradation of methylene blue and rhoda-
continuous decrease in concentration of aqueous solution of mine-B, respectively in presence of cobalt-iron sulfide. Cobalt

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
5
Figure 2. TEM image of cobalt-iron sulfide.
sulfide (Co S ) nanoparticles prepared from tris(N,N-difurfur- and the pure solvent was used as the reference. The NMR
3
4
yldithiocarbamato-S,S’)cobalt(III) were used as catalyst for the spectra were recorded on Bruker 500 MHz NMR spectrom-
degradation of rhodamine-B under ultraviolet irradiation. eter at room temperature in DMSO-d , using TMS as internal
This reference. TEM images were recorded using TECNAI T2 G2
6
[22]
Co3S4 degraded 85% of rhodamine-B in 180 min.
study indicates that as-prepared cobalt-iron sulfide acts as
good catalyst for dye degradation.
make-FEI. EDS were performed by SUPRA 55VP CARL.
Photoluminescence spectra were recorded using Perkin Elmer
1
555 fluorescence spectrophotometer at room temperature.
Mechanism of photodegradation process
Cyclic voltammetric studies
In the presence of air, the irradiated semiconductor nano-
particles are capable of destroying many organic pollutants.
The activation of metal sulfide by UV irradiation produces
electron-hole pairs which are powerful oxidizing and reduc-
ing agents, respectively.
Cyclic voltammetry was performed using a conventional
three electrode system. A glassy carbon (GC) was used as a
working electrode. The counter electrode was a platinum
wire, and reference electrode was Ag/AgCl. The HPLC grade
of dichloromethane was used as the solvent and tetrabuty-
lammonium fluoroborate (0.01 M) as the supporting electro-
þ
ꢀ
CoFeS þ hc ! h þ e
ꢀ
1
lyte. The scan rate was 100 mVs . Complexes 1 and 2 were
The oxidative and reductive reactions are expressed as:
ꢃ
investigated at 25 C in an oxygen-free atmosphere, pro-
ꢀ
þ
ꢀ
ꢀ
2
OH þ h ! OH and O þ e ! O
2
vided by bubbling purified nitrogen through the solution.
ꢀ
4
The concentration of the compounds was 1 ꢂ 10 M and
These hydroxyl radicals degraded the dye molecule and
hence the decolourisation of the solution occurred.
electrochemical solution of (n-Bu N) X (X = I, Br, Cl, F; 5
4
ꢀ
4
ꢂ 10
M) in CH Cl . Cyclic voltammograms were
2 2
recorded on a CHI604C Electrochemical Analyser.
Experimental
Materials and instrumentation
Photocatalytic experiments
All reagents and solvents were commercially available high-
grade materials (Merck/Sd fine/Sigma Aldrich) and used as
received. IR spectra were recorded on a Thermo Nicolet
The photocatalytic activity of cobalt-iron sulfide was eval-
uated by degradation of aqueous solution of methylene blue
and rhodamine-B. All the solutions were prepared using
ꢀ
1
Avatar 330 FT-IR spectrophotometer (range: 4000–400 cm ) double distilled water. A typical photocatalytic experiments,
as KBr pellets. A Shimadzu UV-1650 PC double-beam UV- Catalyst (0.1 g) was added to an aqueous solution of dye (50
ꢀ
4
vis spectrophotometer was used for recording the electronic mL) in the concentration of 1.0 ꢂ 10 M. The solution
spectra. The spectra of complexes were recorded in CHCl3 was maintained under darkness for 30 min to reach dye

6
S. THIRUMARAN AND G. GURUMOORTHY
Figure 3. Time-dependent UV-Vis absorption spectra for decolourization of (a) methylene blue and (b) rhodamine-B using cobalt-iron sulfide under ultraviolet light.
solution adsorption–desorption equilibrium. The solution presence of dithiocarbamate ligands, forming Co(III) tris(dithio-
[
26]
ꢃ
with the suspended nano-photocatalyst was irradiated by carbamate) complexes. Yield: 78%, mp: 155–156 C. IR (KBr,
ꢀ
1
UV light from mercury vapour lamp. At given time inter- cm ): ꢀ = 3380 (ꢀ N-H), 1488 (ꢀC–N), 1027 (ꢀC–S). UV-Vis
3
ꢀ1
ꢀ1
vals, 3 mL of aliquots was withdrawn and centrifuged to (CHCl
, nm): k (e,dm mol ꢄcm ) = 250, 277, 327, 400, 488
3
1
(
52), 642: H NMR (500 MHz, DMSO-d ): d 0.98 (broad, 9H,
remove catalyst, concentration of both dye solution was
determined with the help of UV-vis spectrophotometer.
6
N-CH -CH -CH -CH ), 1.38 (broad, 6H, N-CH -CH -CH -
2
2
2
3
2
2
2
CH ), 1.68 (broad, 6H, N-CH -CH -CH -CH ), 3.65 (6H, N-
3
2
2
2
3
CH -CH -CH -CH ) 4.67- 5.02 (m, 6H, N-CH (pyrrole)), 6.15
2
2
2
3
2
Preparation of amines
(s, 3H, H-3(pyrrole)), 6.20 (s, 3H, H-4, (pyrrole)), 6.81 (s, 3H,
13
H-5(pyrrole)), 9.04 (3H, NH-pyrrole). C NMR (125 MHz,
DMSO-d ): d 13.7 (N-CH CH CH CH ), 20.1 (N-CH -CH -
N-(pyrrol-2-ylmethyl)-N-butylamine and N-methylferro-
cenyl-N-(2-phenylethyl)amine were prepared by general
methods reported earlier.
6
2
2
2
3
2
2
CH -CH ), 28.9 (N-CH -CH -CH -CH ), 44.7 (N-CH -CH -
[
12]
2
3
2
2
2
3
2
2
CH -CH ), 48.1 (N-CH (pyrrole)), 107.8, 109.4, 119.1, 125.6
2
3
2
(
pyrrole ring carbons), 205.6 (NCS ). Anal. Calcd. for
2
C H CoN S , (%): C, 48.62; H, 6.12; N, 11.34; found (%): C,
48.49; H, 6.08; N, 11.24 .
30
45
6 6
Preparation of tris(N-(pyrrol-2-ylmethyl)-N-
butyldithiocarbamato-S,S )cobalt(III) (1)
0
N-(pyrrol-2-ylmethyl)-N-butylamine (3.0 mmol) in ethanol (20
mL) was mixed with carbon disulfide (3.0 mmol, 0.2 mL)
under ice cold condition (5 C). The solution was stirred for
Preparation of tris(N-methylferrocenyl-N-(2-
phenylethyl)dithiocarbamato-S,S )cobalt(III) (2)
0
ꢃ
3
0 min. This produced the (N-(pyrrol-2-ylmethyl)-N-butyldi-
A method similar to that described for the synthesis of
[12]
thiocarbamic acid solution.
An aqueous solution of
1
was adopted; however, N-methylferrocenyl-N-(2-phenyle-
CoCl ꢄ6H O (1.0 mmol, 10 mL) was added to the dithiocarba-
2
2
thyl)amine was used instead of N-(pyrrol-2-ylmethyl)-N-
ꢃ
mic acid solution resulting in the formation of a green precipi- butylamine (Scheme 1) Yield: 84%, mp: 165-166 C. IR
ꢀ
1
tate. The precipitate obtained was filtered, washed several times (KBr, cm ): ꢀ = 1485 (ꢀC–N), 1025 (ꢀC–S). UV-Vis (CHCl3,
with cold water and then air dried (Scheme 1). It was observed nm): k (e,dm mol cm ) = 249, 274, 323, 401, 472 (59),
that Co(II) is converted to Co(III) by aerial oxidation in the 632: H NMR (500 MHz, DMSO-d ): d 2.91 (N-CH -CH -
3
ꢀ1
ꢀ1
1
6
2
2

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
7
C H ), 3.65–4.80 (NCH -CH -C H , N-CH ferrocenyl and
Diacetatedithiocarbamate. Polyhedron. 2014, 80, 233–242. DOI:
0.1016/j.poly.2014.04.045.
2] Kaludjerovic, G. N.; Ojinovic, V. M.; Trifunovic, S. R.; Hodzic,
6
5
2
2
6
5
2
13
1
cyclopentene), 7.24 (broad, 15H, phenyl ring protons)
C
[
NMR (125 MHz, DMSO-d ): d 33.4 (N-CH -CH C H ),
6
2
2
6
5
I. M.; Sabo, T. J. Synthesis and Characterization of trisbutyl-(1-
4
6
1
7.9 (N-CH -CH -C H ), 49.2 (N-CH -ferrocenyl), 68.6,
8.8, 70.1, 80.1 (C-C (ferrocenyl ring carbons) 126.5, 128.6,
2 2 6 5 2
methyl-3-phenyl-propyl)-dithiocarbamato-
cobalt(III)
Seskvitoluene. J. Serb. Chem. Soc. 2002, 67, 123–126.
28.8, 138.3 (phenyl ring carbons), 205.0 (NCS ). Anal.
[3] Abu-El-Halawa, R.; Zabin, S. A. Removal Efficiency of Pb, Cd,
Cu and Zn from Polluted Water Using Dithiocarbamate
Ligands. J. Taiba Univ. Sci. 2017, 11, 57–65. DOI: 10.1016/
j.jtusci.2015.07.002.
2
Calcd. for C H CoFe N S (%): C, 58.02; H, 4.87; N, 3.38;
6
0
60
3 3 6
found (%): C, 58.00; H,4.84; N,3.37.
[
4] Nabipour, H.; Ghammamy, S.; Ashuri, S.; Aghbologh, Z. S.
Synthesis of a New Dithiocarbamate Compound and Study of
Its Biological Properties. Org. Chem. J. 2010, 2, 75–80.
Preparation of cobalt-iron sulfide
[
5] Costa Junior, A. C.; Versiane, O.; Faget Ondar, G.; Ramos,
J. M.; Ferreria, G. B.; Martin, A. A.; Tellez soto, C. A. An
Experimental and Theoretical Approach of Spectroscopic and
2
(0.5 g) was mixed with triethylenetetraamine (15 mL) in a
round bottom flask and then the content of the flask was
refluxed for 15 min. The black precipitate obtained was fil-
tered off and washed with methanol.
Structural
bis(diethyldithiocarbamate)–cobalt(II). J. Mol. Struct. 2012,
029, 119–134. DOI: 10.1016/j.molstruc.2012.06.041.
Properties
of
the
1
[
6] Masek, J.; Ishida, I.; Zogg, H.; Maissen, C.; Blunier, S.
Monolithic Photovoltaic PbS-on-Si Infrared-Sensor array. Array
IEE Electr. Dev. Lett. 1990, 11, 12–14. DOI:10.1109/55.46915.
7] Gong, M.; Kiokeminde, A.; Kumar, N.; Zhao, H.; Ren, S. Ionic-
Passivated FeS2 Photocapacitors for Energy Conversion and
Storage. Chem. Commun. 2013, 49, 9260–9262. DOI: 10.1039/
C3CC45088K.
8] Tokyo, N.; Azkio, K. J Pn. Kokai Pat. 1978 7855478 C1.C23
C15/00.
9] Tokya, N. J Pn. Kokai pat. 1975 75130378 C1 H0 1L CO 1B.
Conclusions
In this contribution two new cobalt(III) dithiocarbamates
containing pyrrole (1) and ferrocenyl (2) units were synthe-
sized and characterized by elemental analysis and spectro-
scopic techniques. UV-vis spectral data are consistent with
the formation of octahedral cobalt(III) complexes. Both the
complexes were evaluated for their ability to sense halide
[
[
[
ions using cyclic voltammetric techniques. Both the com- [10] Asunskis, D. J.; Boltin, I. L.; Rolde, A. T. W.; Zachary, A. M.;
ꢀ
plexes prefer to bind with I . Complex 2 contains redox
active ferrocene moiety is a better sensor compared to those
of 1. Bimetallic sulfide (cobalt-iron sulfide) nanoparticles
were successfully prepared from 2 and characterized by
EDS, TEM, UV-vis, photoluminescence and FT-IR spectros-
copy. Photocatalytic activity of as prepared nanoparticles
was evaluated by degradation of methylene blue and rhoda-
mine-B in aqueous solution under ultraviolet irradiation. It
was found that the as prepared cobalt-iron sulfide is an effi-
cient photocatalyst for the degradation of rhodamine-B. This
study indicates that cobalt(III) dithiocarbamate complexes
Hanley, L. Lead Sulfide Nanocrystal-Polymer Composites for
Optoelectronic Applications. Macromol. Symp. 2008, 268,
33–37. DOI: 10.1002/masy.200850807.
[
[
11] Khalid, S.; Ahmed, E.; Malik, M. A.; Abu bakar, S.; Khan, Y.;
Brien, P. O. Synthesis of Pyrite Thin Films and Transition
Metal Doped Pyrite Thin Films by Aerosol-Assisted Chemical
Vapour Deposition. New. J. Chem. 2015, 39, 1013–1021. DOI:
10.1039/C4NJ01461H.
12] Sathiyaraj, E.; Gurumoorthy, G.; Thirumaran, S. Nickel(II)
Dithiocarbamate Complexes Containing the Pyrrole Moiety for
Sensing Anions and Synthesis of Nickel Sulfide and Nickel
Oxide Nanoparticles. New. J. Chem. 2015, 39, 5336–5349. DOI:
10.1039/c4nj02250e.
can be used for sensing anions and synthesis of bimetallic [13] Pickett, N. L.; Brien, P. O. Syntheses of Semiconductor
Nanoparticles Using Single-Molecular Precursors. Chem. Rec.
sulfide nanoparticles.
2
001, 1, 467–479. DOI: 10.1002/tcr.10002.
[14] Srinivasan, N.; Thirumaran, S. Effect of Pyridine as a Ligand in
Precursor on Morphology of CdS Nanoparticles. Superlattices
Acknowledgments
Microstruct.
2012,
51,
912–920.
DOI:
10.1016/
We are thankful to SAIF, Panjab University, Chandigarh, India, for
recording TEM images.
j.spmi.2012.03.006.
[15] Soltani, N.; Saion, E.; Hussein, M.Z.; Erfani, M.; Abedini, A.;
Bahmanrokh, G.; Navasery, M.; Vaziri, P. Visible Light-Induced
Degradation of Methylene Blue in the Presence of
Photocatalytic ZnS and CdS Nanoparticles. Int. J. Mol. Sci.
Disclosure statement
2
012, 13, 12242–12258. doi: 10.3390/ijms131012242.
No potential conflict of interest was reported by the authors.
[
16] Wada, Y.; Kitamura, T.; Yanaqida, S.; Yin, H. Photoreductive
Dechlorination of Chlorinated Benzene Derivatives Catalyzed
by ZnS Nanocrystallites. Chem. Commun. 1998, 2683–2684.
DOI: 10.1039/A806035E.
Funding
[
17] Rengaraj, S.; Venkatraj, S.; Jec, S. H.; Kim, Y. H.; Tai, C.; Repo,
E.; Koistienen, A.; Ferancova, A.; Sillpaa, M. Cauliflower-like
CdS Microspheres Composed of Nanocrystals and Their
Physicochemical Properties. Langumuir. 2011, 27, 352–358.
DOI: 10.1021/la1032288.
Dr. S. Thirumaran is thankful to University Grants Commission
(UGC), India (F. No. 42-341/2013 (SR)) for providing fund for this
research study. University Grants Commission, India.
[
18] Wong, W. W. H.; Curiel, D.; Lai, S. W.; Drew, M. G. B.; Beer,
References
P. D. Ditopic Redox-Active Polyferrocenyl Zinc(II)
[
1] Leka, Z.; Voja, D.; Kosovic, M.; Latinovic, N.; Dakovic, M.;
Visnjevac, A. Syntheses, Structures and Antifungal Activities of
Novel Co, Mo and Pt Complexes with triammonium N,N-
Dithiocarbamate
Coordination and Electrochemical Recognition Properties.
Dalton Trans. 2005, 774–781. DOI: 10.1039/B416851H.
Macrocyclic
Receptors:
Synthesis,

8
S. THIRUMARAN AND G. GURUMOORTHY
[
[
19] Beer, P. D.; Smith, D. K. Tunable bis(ferrocenyl) Receptors for
the Solution-Phase Electrochemical Sensing of Transition-Metal
Vitro Antitumor Activity. Inorg. Chem. 2005, 44, 1867–1881.
DOI: 10.1021/ic048260v.
Cations. J. Chem. Soc. Dalton Trans. 1998, 417–423. DOI: [25] Lever, A. B. P. Inorganic Electronic Spectroscopy. 2nd ed.;
0.1039/A707278C.
Elsevier: Amsterdam, 1984.
20] Bharati, P.; Bharti, A.; Nath, P.; Bharty, M. K.; Butcher, R. J.; [26] Dulare, R.; Bharty, M. K.; Singh, A.; Singh, A. K. Synthesis,
1
Singh, N. K. Synthesis, Spectral and Structural Characterization
of Cobalt(III) Dithiocarbamato Complexes: Catalytic
Application for the Solvent Free Enamination Reaction.
Spectral and Structural Studies of 1-Ethoxycarbonyl-
Piperazine4-Carbodithioate and its Co(III), Zn(II) and Cd(II)
Complexes. Polyhedron. 2012, 31, 373–378. DOI: 10.1016/
j.poly.2011.09.036.
Polyhedron. 2015, 102, 375–385. DOI: 10.1016/j.poly.2015.
10.007.
[
27] Bond, A. M.; Cotton, R.; Gatehouse, B. M.; Mah, Y. A. Cationic
Silver Compounds with Metal (Co, Rh, Ir) tris(dithiocarbamate)
and tris(diselenocarbamate) Complexes as Ligands: Synthetic,
Electrochemical, NMR, Electrospray Mass Spectrometric and X-
ray Crystallographic Studies. Inorg. Chim. Acta. 1997, 260,
[
[
21] Beer, P. D., Berry, N. G.; Cowley, A. R.; Hayer, E. J.; Oates,
E. C.; Wong, W. W. H. Metal-Directed Self-Assembly of
Bimetallic Dithiocarbamate Transition Metal Cryptands and
Their Binding Capabilities. Chem. Commun. 2003, 2408–2409.
DOI: 10.1039/B308629A.
22] Gurumoorthy, G.; Rani, P. J.; Thirumaran, S.; Ciattini, S.
Cobalt(III) Dithiocarbamates for Anion Sensing and
Preparation of Cobalt Sulfide and Cobalt-Iron Sulfide
Nanoparticles: Photocatalytic Degradation of Dyes with as-pre-
pared Nanoparticles. Inorg. Chim. Acta. 2017, 455, 132–139.
DOI: 10.1016/j.ica.2016.10.011.
61–71. DOI: 10.1016/S0020-1693(96)05551-X.
[
28] Wallace, W. H.; Wong, D. E.; Phipps, P. D.; Beer. Acyclic and
Macrocyclic Transition Metal Dithiocarbamate Complexes
Containing Imidazolium Moieties for Anion Binding.
Polyhedron. 2004, 23, 2821–2829. DOI: 10.1016/j.poly.2004.
06.020.
[
29] Brus, L. Electronic Wave Functions in Semiconductor Clusters:
Experiment and Theory. J. Phys. Chem. 1986, 90, 2555–2560.
DOI: 10.1021/j100403a003.
[
[
23] Cui, H.; Pike, R. D.; Kershaw, R.; Dwight, K.; Wold, A.
Syntheses of Ni3 S2, Co9 S2 and ZnS by the Decomposition of
Diethyldithiocarbamate Complexes. J. Solid State Chem. 1992,
1
01, 115–118. DOI: 10.1016/0022-4596(92)90206-B.
[30] Bhar, S. K.; Jana, S.; Mondal, A.; Mukherjee, N. Photocatalytic
Degradation of Organic Dye on Porous Iron Sulfide Film
Surface. J. Colloid Interface Sci. 2013, 393, 286. DOI: 10.1016/
j.jcis.2012.10.049.
24] Ronconi, L.; Giovagnini, L.; Marzano, C.; Bettio, F.; Graziani,
R.; Pilloni, G.; Fregona, D. Derivatives as Potential
Antineoplastic Agents: Design, Spectroscopic Properties, and in