Tetrakis(ethyl-4(4-butyryl)oxyphenyl)porphyrinato zinc complexes with 4,4′-bpyridin: Synthesis, characterization, and its catalytic degradation of Calmagite

Article abstract of DOI:10.1039/c8ra01134f

This work reports on the synthesis and characterization of a new porphyrins complex:[Zn(TEBOP)(4,4′-bpy)](4,4′-bipyridine)(5,10,15,20-(tetraethyl-4(4-butyryl)oxyphenyl)porphyrinato)zinc(ii) (3). Single crystal X-ray diffraction, photophysical and electroc

Full text of DOI:10.1039/c8ra01134f

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PAPER
Tetrakis(ethyl-4(4-butyryl)oxyphenyl)porphyrinato
0
zinc complexes with 4,4 -bpyridin: synthesis,
Cite this: RSC Adv., 2018, 8, 20143
characterization, and its catalytic degradation of
Calmagite†
ac
b
d
c
Raoudha Soury, Mahjoub Jabli, Tawfik A. Saleh, * Wathiq Sattar Abdul-Hassan,
c
c
e
a
Eric Saint-Aman, Frederique Loiseau, Christian Philouze and Habib Nasri
´
´
0
This work reports on the synthesis and characterization of a new porphyrins complex:[Zn(TEBOP)(4,4 -
0
bpy)](4,4 -bipyridine)(5,10,15,20-(tetraethyl-4(4-butyryl)oxyphenyl)porphyrinato)zinc(II) (3). Single crystal
X-ray diffraction, photophysical and electrochemical characteristics were studied. The prepared
complex, penta-coordinated zinc(II) porphyrin derivatives shows moderate ruffling distortion and the zinc
atom is nearly planar with the porphyrin core. Tolyl and ethyl-4(4-butyryl)oxyphenyl) moieties at the
meso positions present a bathochromic shift of the absorption bands, and a notable increase in the
absorption coefficient of the Q(0,0) and Q(0,1) bands was observed with a higher fluorescence quantum
yield and lifetime compared with the free base porphyrin. The electrochemical investigation shows
a reversible reduction of the synthesized complexes. The catalytic power and the adsorption properties
of the prepared complexes were studied for Calmagite degradation, an azoic organic dye. The results
reveal that the studied compounds could be used as catalysts for the decolourisation of dyes in the
Received 6th February 2018
Accepted 1st May 2018
DOI: 10.1039/c8ra01134f
rsc.li/rsc-advances
2 2
presence of H O .
ambiguities in the coordination numbers, spin states and
oxidation states, Zn synthetic porphyrin complexes are used
1
. Introduction
2
+
Owing to their interesting photochemical and photophysical as models to examine the effect of the axial ligation on the
properties, zinc porphyrin complexes have attracted increasing properties of the metalloporphyrins. In this framework, several
1
–3
attention. Indeed, their advantages make them useful for investigations on ve coordinated zinc porphyrin types
various applications such as Organic Light Emitting Diodes [Zn(Porph)(L)] where Porph is a meso-porphyrin and L is
4
(
OLEDs), materials, photodynamic therapy, photodynamic a monodentate neutral or anionic axial ligand, have been re-
5–8
9
10–12
13–15
destruction of viruses, chemical sensors, photovoltaic,
etc. In particular, zinc metalloporphyrins remain to be used as porphyrins with imidazole and pyridine axial ligands are known
models to understand the electronic properties, the uores- to be around 10 . It is noteworthy that even though the Zn
ported in the literature.
The association constants of zinc
4
16
2+
cence spectra and the redox properties of hemoproteins and ion in the porphyrin center has a marked preference for ve-
bacterial photosynthesis. To avoid complications introduced by coordinate square-pyramidal geometry, few examples of six-
2
+
3+
partially lled d orbital metal ions such as Fe and Co and coordinated zinc porphyrin complexes are known in
17,18
solution.
Several investigations involving zinc porphyrins with aza
a
Laboratory of Physico-Chemical of Materials, Faculty of Sciences of Monastir,
19–23
ligands have been reported.
These studies concern bis(zinc-
University of Monastir, 5000 Monastir, Tunisia
b
porphyrin) tweezers and were aimed to design and study the
Textile Materials and Process Research Unit, ENIM, University of Monastir, 5000
Monastir, Tunisia
photoactive multicomponent systems which lead to the
c
24,25
Department of Molecular Chemical, UMR CNRS 5250, ICMG-FR 2607, Laboratory of understanding of the bacterial photosynthesis.
Zinc
Inorganic Chemistry, University J. Fourier, R ´e dox, 301 Rue de la Chimie, BP 53-38041,
0
porphyrins studies with 4,4-bipyridine (4,4 -bpy) axial ligand are
Grenoble Cedex 9, France
very limited and are specically concerned with dimers and
d
Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran
18
trimmers. This bidentate ligand is known to be involved in the
3
1261, Saudi Arabia. E-mail: tawk@kfupm.edu.sa; tawkas@hotmail.com
18,26,27
e
building blocks of supramolecular structures.
However,
Department of Molecular Chemicals (CNRS/UGA) B aˆ timent chimie recherche,
domaine Universitaire, 301 rue de la chimie, Saint-Martin-d'Heres, Gieres, CS a survey of the literature reveals that no reported photophysical
0
4
†
1
0700, 38058 Grenoble CEDEX 9, France
studies concerning zinc metalloporphyrins with the of 4,4 -bpy
Electronic supplementary information (ESI) available: CCDC 1060414. See DOI:
0.1039/c8ra01134f
ligand and a very few reported works on the tetrakis(ethyl-4(4-
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28,29
31
butyryl)oxyphenyl)porphyrin (H
2
TEBOP) are known.
Herein, meso-porphyrin was achieved as described in the literature,
in the present work, we describe the synthesis of the starting leading to the formation of the [Zn(TEBOP)] complex (2).
0
materials H TEBOP porphyrin (1), the two new complexes: [Zn(TEBOP)] (2) (20 mg, 0.020 mmol) and 4,4 -bipyridine
2
[
5,10,15,20-(tetraethyl-4(4-butyryl)oxyphenylporphyrinato)]zin-
(80 mg, 0.5 mmol) were dissolved in 5 mL of dichloromethane
0
c(II) [Zn(TEBOP)] (2) and (4,4 -bipyridine)[(5,10,15,20-(tetraethyl- then the solution was stirred overnight leading to the penta-
4
0
0
(4-butyryl)oxyphenyl)porphyrinato)]zinc(II) [Zn(TEBOP)(4,4 - coordinated complex [Zn(TEBOP)(4,4 -bipy)] (3). Dark purple
bpy)] (3). The H TEBOP (1) is a meso-porphyrin presenting four crystals 3 (Fig. 2) was obtained by slow diffusion of n-hexane
2
ethyl-4(4-butyryl)oxyphenyl groups (arms) at the meso-positions. into the dichloromethane solution (in 85% yield). The obtained
The molecular structure, along with the spectroscopic and compound was characterized by NMR spectroscopy, mass
electrochemical studies were reported. The effect of the axial spectrometry and elemental analysis. Anal. calc. for
3
ꢀ1
ligand and the groups at the meso-position on the electronic C H N O Zn (1354.87 g mol ) C, 69.14; H, 5.65; N, 6.20%.
7
8
76 6 12
properties of the metalloporphyrin were assessed. Their sorp- Found: C, 69.62; H, 5.48; N, 6.38%. UV/Vis [CH Cl , l in nm
max
2
2
ꢀ
1
tion capacities and catalytic degradation were studied using (log 3)]: 430 (5.33), 563 (4.00), 604 (3.59). IR (cm ): 3037: n
Calmagite dye. [CH(bpy)]; 1580: n[(CN)bpy]; 1727: n(C]O); 1606: n(C–O); 993: d
+
[
[
8
CCH(TEBOP)]. MS (ESI , dichloromethane): m/z ¼ 1354.8
0
+ 1
Zn(TEBOP)(4,4 -bpy)] . H NMR (300 MHz, CDCl
.85 (s, 8H, Hb-pyrro); 8.45 (d, 8H, Ho,o ); 7.19 (d, 8H, Hm,m ); 6.22
3
) d (ppm) ¼
2. Experimental
0
0
2.1. Reagents
(
s, 4H, H ); 5.60 (d, 4H, H ); 4,29 (q, 8H, H ); 4,22 (t, 8H, H );
2
1
a
d
The used reagents (K
2
CO
3
, NH
4
Cl, etc.) and solvents (dichloro- 2,68 (t, 8H, H
c
); 2,30 (qi, 8H, H
b
); 1,35 (t, 15H, H ).
e
methane, chloroform, N,N-dimethylformamide, etc.) were ob-
tained from Sigma Aldrich and were used as received without
further purication. The chemical structure of Calmagite dye
2
.3. Characterization
ꢀ1
1
(
molecular weight ¼ 358.37 g mol , wavelength ¼ 526 nm) is
H NMR spectra were recorded on a Bruker 300 Ultrashield
spectrometer. UV/vis measurements and titration were per-
formed on a WinASPECT PLUS (validation for SPECORD PLUS
version 4.2) scanning spectrophotometer. Solutions of porphy-
rins were prepared in spectrophotometric grade dichloro-
methane (Sigma-Aldrich). Mass spectra were recorded with
a MicrOTOF Q Bruker instrument (ESI, positive mode).
given in Fig. 1.
2
.2. Synthesis
.2.1. Synthesis of ethyl-4(4-butyryl)oxyphenyl. Under an
inert atmosphere of 4-hydroxybenzaldehyde (6.0 g, 49.1 mmol)
and 13.6 g of K CO (13.6 g, 98.2 mmol) were dissolved in 40 mL
2
2
3
2.3.1. Absorption and emission properties. Electronic
of N,N-dimethylformamide (DMF). Then, 7 mL of ethyl 4-bro-
absorption spectra were recorded on a Cary 300 UV-visible
spectrophotometer (Agilent Technologies, Santa Clara, CA).
Emission spectra were recorded in dichloromethane at room
temperature on a Horiba Scientic Fluoromax-4 spectrouo-
rometer. Samples were placed in 1 cm path length quartz
cuvettes. Luminescence lifetime measurements were performed
aer irradiation at l ¼ 400 nm obtained by the second
harmonic of a titanium: Sapphire laser (picosecond Tsunami
laser spectra physics 3950-M1BB + 39868-03 pulse picker
doubler) at an 800 kHz rate of repetition. For the decay acqui-
sition, Fluotime 200 (AMS technologies) was utilized consisting
of a GaAsmicro channel plate photomultiplier tube (Hama-
matsu model R3809U-50) followed by a time-correlated single
photon counting system from Picoquant (PicoHarp300). The
ultimate time resolution of the system is close to 30 ps. Lumi-
nescence decays were analyzed with FLUOFIT soware available
from Picoquant. Emission quantum yields were determined at
room temperature in dichloromethane solutions using the
mobutyrate (9.6 g, 49.1 mmol) was added to the solution. The
reaction mixture is heated at 80 C under argon overnight and
the reaction was checked using CCM plates. Aer ltration of
ꢁ
the K
taken up in dichloromethane (CH
a saturated NH Cl solution. This was followed by washing with
distilled water three times. Finally, the crude was puried.
11.13 g, 91.18 mmol) of aldehyde was obtained in 96% yield;
2
CO
3
, the DMF was evaporated. The crude obtained was
2
2
Cl ) and then washed with
4
(
1
light yellow liquid: H-NMR (CDCl
1
4
3
, 300 MHz): d (ppm) ¼ 9,89 (s,
0
0
H, Hald); 7,82 (d, 2H, Ho,o ); 6.99 (d, 2H, H
,12 (q, 2H, H ); 2,55 (t, 2H, H ); 2,17 (qi, H ); 1,29 (t, 3H, H )
); 4,17 (t, 2H, H );
m,m
a
d
c
b
e
(
Fig. S1–S3†).
.2.2. Synthesis of [Zn(TEBOP)(4,4 -bipy)] (3). The meso-
porphyrin H TEBOP (1) was prepared according to the Adler
0
2
2
30
and Longo method. The incorporation of the zinc into this
32
optically dilute method. . [Zn(TPP)] in air-equilibrated
dichloromethane solution was used as quantum yield stan-
dard (F ¼ 0.031). The instrumental uncertainties are as follows:
absorption maxima 2 nm; molar absorption, 20%; emission
maxima, 5 nm; emission lifetimes, 10%; emission quantum
yields, 20%.
2.3.2. Cyclic voltammetry. Cyclic voltammetry (CV) experi-
ments were carried out using a CH-660B potentiostat (CH-
instrument). The analytical experiments were conducted at
Fig. 1 Chemical structure of Calmagite.
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Fig. 2 Molecular structure of zinc meso-porphyrin complex 3.
room temperature under an argon atmosphere (argon stream) at 200 K for 3. Reexions were scaled and collected for
in standard one-compartment, three-electrode electro- absorption effects using SADABS programs (Bruker AXS
a
33
chemical cell. Tetra-n-butyl ammonium perchlorate (TBAP) was 2004, ), the structure of 3 was solved bya direct method using
used as a supporting electrolyte (0.2 M) in dichloromethane SIR-2004 (ref. 34) and rened by full-matrix least-squares on F
2
35
previously distilled over calcium hydride under argon. An using the SHELXL-97 program.
The SIMU/DELU/SADI
36
automatic ohmic drop compensation procedure was systemat- restraint commands in the SHELXL-97 soware were used.
ically implemented prior to recording the CV data in electrolytic For complex 3, one fragment in meso position of the TEBOP
solutions containing the studied compound at a concentration porphyrin, made by an ethyl-4-phenoxybutanoate group, is
ꢀ
3
ꢂ 10 M. CH-instrument vitreous carbon (F ¼ 3 mm) working disordered over two orientations with rened occupancy coef-
electrodes were polished with 1 mm diamond paste before each cients converged to 0.559(5) and 0.441(5) respectively. The ADP
+
ꢀ2
recording. The Ag/Ag (10 M + TBAP 0.2 M in CH Cl ) redox values of this fragment are quite high. Thus, DFIX, DELU/SIMU,
2
2
35
couple was used as a reference electrode. The potential of the SIMU/ISOR and FLAT restraints and the EADP constraint
ferrocene/ferrocenium redox couple used as an internal refer- commands in the SHELXL-97 soware were used which
+
ꢀ2
ence is of 86 mV vs. Ag|Ag (10 M) under our experimental explains an important number of restraints (Table S1†). The H-
conditions. For comparison with previously published data, all atoms in 3 were included at estimated positions using a riding
potentials given in the text were converted to SCE using E vs. model. The non hydrogen atoms of 3 were rened with aniso-
+
ꢀ2
SCE ¼ E vs. Ag/Ag (10 M) + 298 mV.
.3.3. X-ray diffractometry. Data collection for 3 measure-
ments was done using a Brucker-AXS Enraf-Nonius Kappa CCD.
tropic thermal parameters.
2
2.4. Oxidative degradation and adsorption experiments of
This
diffractometer
monochromated MoK
was
equipped
with
˚
graphite-
Calmagite
a
radiation (l ¼ 0.71073 A) and intensity
data for 3 was collected by the narrow frame method at room The catalytic experiments were conducted using 12 mg, of the
temperature. Unit cell parameters were calculated and rened studied catalyst with 20 mL of Calmagite solution in the pres-
from the full data set. The measurements of the data were done ence of a calculated dose of H O (4 mL L ). Experiments were
ꢀ
1
2
2
0
Fig. 3 The coordination environment of Zn(II) and structure conformation of [Zn(TEBOP)(4,4 bpy)]. Ellipsoids are drawn at 30% probability.
Symmetry codes are (i) ¼ ꢀx + 1, y, ꢀz + 3/2.
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performed in a batch system and were uniformly agitated at
a speed of 150 rpm till the equilibrium is reached. At the end of [Zn(TEBOP)(4,4 -bpy)] complex. The zinc(II) center metal is
The asymmetric unit of
3
is made by
a
one half
0
each contact time, the solutions were ltered using a Whatman chelated by four pyrrole N atoms of the porphyrinato anion and,
0
No. 41 lter paper. The concentration of dye in each ltrate was additionally coordinated by a nitrogen atom of the 4,4 -bipyr-
determined at the maximum wavelength (526 nm). The idine axial ligand in a distorted square-pyramidal geometry. As
0
adsorption experiments were carried out under the same depicted in Table S2,† the Zn_N(4,4 -bpy) bond length is
˚
˚
conditions without the addition of the oxidizing agent.
2.151(2) A which is in the range [2.144–2.490 A] of the related
4
0
,4 -bpyporphyrinic and non-porphyrinic zinc(II) species (Table
S3†).
The average equatorial distance between the zinc cation and
the nitrogen atoms of the porphyrin macrocycle(Zn-Np) is
3
. Results and discussion
3.1. X-ray crystallography of complex 3
˚
2
.0675(3) which is in the range [2.030–2.081 A] of other reported
0
Single crystals of complex 3 were obtained by slow diffusion of Zn(II)-(4,4 -bpy) porphyrins (Table S3†).
n-hexane into their dichloromethane solution. The structure of
Fig. S2a and b† show the a and b dihedral angles of 3 while
complex 3 was solved by X-ray crystallographic analyses. Fig. S2† illustrates the coordination geometry of the zinc atom
Complex 3 crystallizes in the monoclinic system (C2/c) space of this derivative. a is the dihedral angle between the “N -M-N ”
p L
group. The crystal parameters are given in Table S1† and plan (Np is the closest pyrrole nitrogen atom) and the rst
0
selected bond lengths and angles are given in Table S2.† The pyridyl moiety of the 4,4 -bipyridine axial ligand. b represents
0
ORTEP drawing of this complex is shown in Fig. 3.
the dihedral angles between the two pyridyl rings of the 4,4 -
Fig. 4 Formal diagram of the porphyrinato core of complex 3 illustrating the displacements of each atom from the 24-atoms core plane in units
of 0.01 A˚ .
0
Fig. 5 Drawing showing part of the lattice packing of the [Zn(TEBOP)(4,4 -bpy)] complex.
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1
Fig. 6 Selected H NMR data (d in ppm) of complex 3.
ꢁ
ꢁ
0
0
bipyridine. The values of a and b of 3 are 36 and 37 , respec- spectrum of 3 is given in (Fig. S5†). It is noteworthy that the 4,4 -
tively, which are close to those of other reported 4,4 -bpypor- bpy protons of compound 3 feature a signicant upeld shi
phyrinic and non-porphyrinic zinc complexes recorded in mainly due to the anisotropic ring current effect of an adjacent
(
Table S3†).
phenyl group of the terminal ligand, dH ¼ 5.60 and dH ¼ 6.22
1
2
Fig. 4 represents the formal diagram of the porphyrinato (Fig. S1†).
core of 3. This diagram reveals that for our synthetic compound,
˚
the zinc atom is displaced by 0.29 A, toward the axial ligand.
3
.3. UV-visible investigation
This species presents a moderate ruffling distortion, as indi-
cated by the displacement of the meso carbons above and below
the porphyrin core. This distortion reects the interaction
between the TEBOPporphyrinato and the 4,4 -bpy ligands, as
well as the orientation of the two pyridyl groups of the axial
ligand.
Porphyrins and metalloporphyrins display two types of
absorption bands, i.e. the intense band in the range [417–424
nm] known as the Soret band, and four weaker bands in the
range [500–700] for free base porphyrins and two weaker bands
37
0
[O(0,0) and (O(1,0)] residing between 500 and 650 nm for met-
alloporphyrins. The UV-visible spectra of 1–3 are illustrated in
The crystal packing of 3 is made by 2D chains, in the (a,c)
plane, where the nearby [Zn(TEBOP)(4,4 -bpy)] complexes are in
0
up-side-down positions. These planes are sustained by weak C–
H/Cg p intermolecular interactions involving Cg pyrrole,
phenyl and pyridyl centroid rings (Fig. 5, Table S4†).
1
3
.2. H NMR spectroscopy
1
The H NMR spectrum of 3 is given in (Fig. S4†) and selected
chemical shi values of this coordination complex along with
a schematic representation of our synthetic species are depicted
in Fig. 6. The b-pyrrolic protons (H ) of the TEBOP moiety are
b
downeld shied (d ꢂ 8.85 ppm). The ortho and meta protons
0
0
(
H
o,o /Hm,m ) present chemical shi values at 8.12/7.24 ppm.
0
The protons H
1
and H
2
of the 4,4 -bpy resonate between 5 ppm
and
7
ppm which is the case of the related species
0
[Zn(TClPP)(4,4 -bpy)] (TClPP
¼
tetrakis(4-chlorophenyl)por-
38
phyrinato) where the H and H protons appears in the same
1
2
domain. This is not the case of the [Zn(Porph) (4,4-bpy)] dimer
2
Fig. 7 UV/Vis absorption spectra of H
2
TEBOP (1), [Zn(TEBOP)] (2) and
38
(
Porph ¼ TClPP and TPP) where the H
1
and H
2
proton are
0
[
Zn(TEBOP)(4,4 -bpy)] (3). In dichloromethane solutions at concen-
1
3
ꢀ5
upeld shied compared to complex 3. The C DEPT NMR trations of ca. 10 M.
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a
0
Table 1 UV/Vis data of H TEBOP (1), [Zn(TEBOP)] (2), [Zn(TEBOP)(4,4 -bpy)] (3) and several related porphyrins and zinc metalloporphyrins
2
Compound
Soret band l (nm) (log 3)
Q bands l (nm) (log 3)
Eg-op
Ref.
a
H
H
H
2
2
2
TEBOP (1)
422(5.47)
—
416 (6.10)
424(5.34)
421
430(5.33)
428
428
517(3.97), 554(3.90), 593(3.67), 651(3.82)
—
513 (5.70) 550 (4.36) 590 (4.24) 646 (4.19)
552(4.03), 594(3.70)
550, 586
563(4.00), 604(3.59)
562 602
562, 604
1.847
1.83
—
2.034
—
2.023
—
—
Current work
42
43
Current work
44
Current work
13
45
a
TPPa
TPP
a
[
[
[
[
[
Zn(TEBOP)] (2)
a
Zn(TTP)]
0
a
Zn(TEBOP)(4,4 -bpy)] (3)
Zn(TPP)(py)]
Zn(TPP)(Him)]
b
b
a
b
In dichloromethane. In toluene, Him: 1-methyl-imidazole, Py: pyridine.
2
0
Fig. 8 Plots of (aE) versus photon energy E of H
2
TEBOP (1), [Zn(TEBOP)] (2) and [Zn(TEBOP)(4,4 -bpy)] (3). a is the absorption coefficient.
0
Fig. 7. The redshi of the Soret and Q absorption bands is clearly indicate equilibrium between 4,4 -bpy and Zn(II) in
related mainly to the non-planar distortion of the porphyrin [Zn(TEBOP)] complex (Fig. 10).
3
9
macrocycle. The values of the Soret and the Q bands of
The results related to the coordination of an N-donor ligand
0
H TEBOP, [Zn(TEBOP)] and [Zn(TEBOP)(4,4 -bpy)], along with such as pyridine or imidazole to zinc(II)porphyrin (Table 2)
those of other porphyrin derivatives, are summarized in Table 1. agree with those previous studies.
2
46,47
Five-coordinated zinc(II)
40,41
3
.3.1. Optical gap. We used the Tauc plot method
to meso-porphyrins with neutral N-donor axial ligand complexes
determine the optical gap energy (Eg-op). Fig. 8 illustrates the present Soret and Q bands red shied vis- `a -vis the starting
2
variation of (aE) versus the photon energy. The values of Eg-op material [Zn(Porph)] (Porph ¼ meso-porphyrin) species were
14
are 1.847, 2.034 and 2.023 eV for 1–3, respectively indicating explained by Chia-ling Lin and coworkers. These researchers
that the gap energy of the metallized species 2–3 are signi- attribute this phenomenon to a destabilization of the HOMO
cantly higher than those of the free base porphyrin (Table 1).
a2u molecular orbital of the porphyrin arising from a ow of
2
+
3
.3.2. UV-vis titration. To study the behavior of the charge from the axial ligand to the porphyrin ring through Zn .
0
[
Zn(TEBOP)] starting material upon addition of 4,4 -bpy to The titration data were tted using the non-linear regression
estimate the value of the association constant(K ) of the analysis program GWBASIC. The determined values of Kas for
as
0
[
Zn(TEBOP)(4,4 -bpy)] complex, the investigation by UV/vis complex 3 are listed in Table 2 along with those of some other
spectroscopy was carried out in dichloromethane with concen- ve-coordinated zinc(II) porphyrins with N-donor axial ligands.
ꢀ
6
ꢀ5
trations of about 10 M for the Soret region and 10 M for the This type of plot suggests a simple binding process with the
48
Q bands region. The titration spectra are presented in Fig. 9a formation of a 1 : 1 (ZnPorph : L) complex. The complex 3
and b for the Soret and the Q bands regions, respectively. The showed the smallest value of the association constant. This
accumulated data are shown in Table 2.
trend could be explained by the stronger electron-donating
0
Incremental amounts of 4,4 -bpy to the solution of [Zn(TE- ability due, mainly, to the presence of alkoxy chains in para-
BOP)] resulted in a Soret band shi of Dl ¼ 8 nm with one position of the phenyl rings of the TEBOPporphyrinato ligand
distinct isobestic point at 426 nm. In the Q bands region, the compared to the related zinc(II) N-donor meso-porphyrins, such
0
13
titration of [Zn(TEBOP)] with the 4,4 -bpy shows a bathochromic as meso-tetratolylphenylporphyrin (TTP)
and the meso-
14
shi of about 12 nm between the starting material [Zn(TEBOP)] tetrakis(2,4,6-trimethylphenylporphyrinato TMP) presenting
and the [Zn(TEBOP)(4,4-bpy)] product with isobestic points at a CH
59 : 582 : 594 nm for the TEBOP derivatives. These results
3
group in para position of the porphyrin phenyl rings.
For our zinc(II)-4,4 -bpy TEBOP derivative, the alkoxy chains
increased the electronic density of the zinc(II) metal ion leading
0
5
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ꢀ6
Fig. 9 Changes in the absorption spectra (a) (Soret band spectral region) of [Zn(TEBOP)] (ꢂ10 M) and recorded in dichloromethane, upon
0
ꢀ5
addition of 4,4 -bpy. Inset: the changes at 428 nm with a 1 : 1 fit (0–5000 equiv.) and (b) UV/vis titration (Q region) of [Zn(TEBOP)] (ꢂ10 M)
0
recorded in dichloromethane, upon addition of 4,4 -bipy (0–400 equiv). Inset: the changes at 563 nm for [Zn(TEBOP)] with a 1 : 1 Zn-porph/
ligand fit.
Table 2 UV/Vis data of complex 3 and selected meso-porphyrins and zinc meso-porphyrins
Compound
Soret band l (nm) (log 3)
Q bands l (nm) (log 3)
log Kas
Ref.
H
H
2
TTP
TEBOP (1)
416(6.10)
422(5.47)
419
420
424(5.34)
420
430(5.33)
428
428
428
428
513(5.70), 550(4.36), 590(4.24), 646(4.19)
517(3.97), 554(3.90), 593(3.67), 651(3.82)
547, 585
550, 586
552(4.03), 594(3.70)
550, 584
—
—
—
—
—
—
15
a
2
Current work
14
14
Current work
14
Current work
13
45
45
45
14
14
14
[
[
[
[
[
[
[
[
[
[
[
[
Zn(TPP)]
Zn(TMP)]
Zn(TEBOP)] (2)
Zn(TDCPP)]
Zn(TEBOP)(4,4 -bpy)] (3)
Zn(TPP)(py)]
Zn(TPP)(Him)]
a
b
0
a
563(4.00), 604(3.59)
3.59 ꢃ 0.2
c
c
c
d
562 , 602
4.33
c
562, 604
564, 604
564, 604
564, 605
567, 606
567, 603
4.8 ꢃ 0.2
5.3 ꢃ 0.2
5.4 ꢃ 0.2
4.71
4.28
5.71
d
Zn(TPP)(1-MeIm)]d
Zn(TPP)(2-MeIm)]
Zn(TPP)(Him)]
Zn(TMP)(Him)]
429
431
431
b
Zn(TDCPP)(Him)]
a
b
c
d
In dichloromethane. TDCPP: is the dianion of the tetra(2,6-dichlorophenyl) porphyrin. In toluene. In cyclohexane.
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0
Fig. 10 Schematic representation of the equilibrium reaction between the 4,4 -bpy ligand and the [Zn(TEBOP)] complex.
0
Fig. 11 The fluorescence spectra of H
a concentration ꢂ 10 M.
2
TEBOP, [Zn(TEBOP)] and [Zn(TEBOP)(4,4 -bpy)] species. Spectra were recorded in CH
Cl
2 2
with
ꢀ6
to the decrease of the coordination character of Zn(II) vis-a-vis in the [380–440 nm] regions. (ii) The strong Q bands assigned to
0
the 4,4 -bpy. Our results agree well with those found by Lin the S
1
/ S
0
transitions. The vibronic origins and overtones
14
et al., where the calculated association constants decrease in (mainly the skeleton vibration) superpose on the electronic
the order TDCPP > TPP > TMP for [Zn(Porph)(L)] complexes excitation.
(
Porph ¼ TPP, TMP and TDCPP (tetra(2,6-dichlorophenyl)
The uorescence spectra of the Zn(II) complexes and the free
ꢁ
porphyrinato) and L ¼ imidazole or 2-methylimidazole). The base porphyrin, recorded at 25 C, are shown in Fig. 11. They
enhanced binding constant for the TDCPP derivative (log Kas
.11) is interpreted in terms of the electrophilicity induced by tions, in the range of [550 750 nm]. The values of the uores-
the electron-withdrawing chlorine substituents in the porphyrin cence of the Q(0,0) and Q(0,1) bands, the uorescence quantum
ꢂ
consist of two bands assigned as the Q(0,0) and Q(0,1) transi-
5
14
core.
yields (4
gathered in Table 2 mentioned above. In addition, the major
difference between the free base H TEBOP compared to those
f f
) and the uorescence lifetimes (s ) of the species are
3
.4. Fluorescence investigation
2
zinc complexes 2–3 is that the two uorescence bands are blue-
shied (Dl z 55 nm for Q(1,0) and Dl z 70 nm for Q(0,0)). This
remarkable blue shi is due to the metal coordination. This
hypsochromic effect is in contrast with the red-shi in the
absorption. For the 2 and 3 complexes, the values of lmax of the
Porphyrins are considered to be the most interesting compound
from the aspects of photophysical properties, owing to their
rigidity and aromatic electronic system. Indeed, they are char-
acterized by two types of uorescence: (i) the relatively weak
49
2 0
Soret or B bands assigned to the S / S transitions, observed
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Table 3 Emission data of several meso-porphyrin and a selection of zinc meso-metalloporphyrins
Compound
Q(0,0), Q(0,1) (nm)
f
f
s
f
(ns)
Solvent
Ref.
meso-Porphyrins
H
H
2
TPP
656, 717
657, 720
0.09
0.035
—
8.0
CH
CH
2
Cl
Cl
2
50
2
TEBOP
2
2
Current work
meso-Porphyrin zinc(II) complexes
[
[
[
[
[
[
Zn(TPP)]
Zn(TEBOP)]
Zn(TEBOP)(4,4 -bpy)] (3)
597, 647
603, 651
603, 651
611, 652
602, 656
604, 655
0.037
0.030
0.028
0.021
—
1.9
1.2
1.2
—
1.9
1.8
CH
CH
CH
CH
Ethyl acetate
Dioxane
2
2
2
2
Cl
Cl
Cl
Cl
2
2
2
2
50
Current work
Current work
45
31
17
0
a
Zn(TTP)(mbpyꢂpy)]
b
Zn(TPP)(IQNO)]
Zn(TPP)(1,4-dioxane)
2
]
—
a
0
0
b
mbpyꢂpy ¼ 4 -Methyl-4-(2-(4-pyridyl)ethenyl)-2,2 -bipyridine. IQNO ¼ isoquinonine N-oxide.
Q(0,0) and the Q(0,1) bands are practically the same, showing of the nature of the meso-porphyrin and the axial ligand. Since
0
that the axial ligand has no effect on this shi. The values of the the 4,4 -bpy ligand has practically no effect on the photophysical
Q(0,0) and Q(0,1) bands of 1–3 are close to those of the related properties of complex 3, one wonders if the para substitution of
zinc porphyrin derivatives (Table 3).
the phenyl ring of the meso-porphyrin on this derivative of this
The Stokes shis for compounds 1–3. This is typical of species has any effect on the uorescence quantum yields and
a uorescence emission having no signicant conformation the uorescence lifetimes values. These two photophysical
variation between the fundamental and the excited states.
parameters depend usually on the exibility of the molecule.
In brief, the s value of the free base porphyrin (8 ns) is, as Indeed, the radiation less deactivation increases with the exi-
f
expected, much higher than those of the [Zn(TEBOP)] and bility of the molecule, which leads to the loss of the “motion
0
[
Zn(TEBOP)(4,4 -bpy)] complexes which are ꢂ1.2 ns.
energy”. This has a direct consequence on the decrease of the
The presence and the nature of the axial ligand have no effect values of F and s . In our case, the TEBOP porphyrinato has an
f
f
on the value of s . Indeed, for [Zn(TPP)] and the related species ethyl-4-phenoxybutanoate group in the para position of the
f
[
Zn(TPP)(IQNO)](IQNO
¼
isoquinoline
values are ꢂ1.9 ns.
N-oxide)
and porphyrin phenyl rings, which is responsible for the important
17,31
[Zn(TPP)(1,4-dioxane) ], the s
2
f
This is the exibility of this porphyrin. Indeed, for the [Zn(TPP)(1,4-
case for our prepared derivative where the s
f
values of [Zn(TE- dioxane)
are the same (1.2 ns). For the value for our TEBOP derivative (3) (1.2 ns).
TEBOP, the uorescence quantum yields are
higher than those of the 2–3 which are within the range [2–4%] of
2 f
] complex, the s value is 1.8 which is much higher than
0
17
BOP)] and [Zn(TEBOP)(4,4 -bpy)] (3) s
the free base H
f
2
15,24
other related zinc-metalloporphyrins.
This indicates that for 3.5. Electrochemistry
the zinc(II) meso-porphyrins, s values are generally independent
ꢀ3
f
The cyclic voltammetry (CV) curve of complex 3 (ꢂ10 M) was
recorded using 0.2 M CH Cl solution of a tetra-n-butyl
2
2
ammonium perchlorate (TBAP) as a supporting electrolyte
Fig. 12). The electrochemical data for the free base H TEBOP
and zinc complexes are summarized in Table S5†. The E1/2
values of the H TEBOP corresponding to one electron reversible
reduction and oxidation are very close and are in the range of
(
2
2
51
2
those of the meso-tetraphenyl porphyrin (H TPP)]. Metallation
of this porphyrin in [Zn(TEBOP)] leads to a shi to more
negative values for the reduction and oxidation characteristic
14,52
potentials.
As expected, the E1/2 values of the [Zn(TEBOP)]
derivatives are inuenced by the electronic properties of the
substituents of phenyl groups; the substitution with electron-
donating groups leads to a negative shi of the characteristic
potentials. Accordingly, the E1/2 values of the tetra-coordinated
zinc-porphyrins are in the order [Zn(TEBOP)] < [Zn(TTP)],
[Zn(TEBOP)] being the easiest to be oxidized in this series. The
opposite shi (Table S5†) was observed with electron-
0
withdrawing substituents such as in the Zn complexes with
Fig. 12 CV curves of [Zn(TEBOP)(4,4 -bpy)]. The solvent is CH
Cl
2 2
and
ꢀ
3
ꢀ1
the tetrapentauoro phenyl porphyrin (H
2
TPFPP) and the
the concentration is ꢂ10 M in 0.2 M TBAP, 50 mV s , WE VC (F ¼ 3
14
mm).
tetra(2,6-dichlorophenyl)porphyrin (H TDCPP).
The
2
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Fig. 13 (a) Change in C
t
/C
0
versus time using a different combination of products: complex 1–Calmagite, complex 3–Calmagite, H
2 2
O –
Calmagite and complex 3–H
complex 3–H
2 2
O –Calmagite (b) change in the maximum absorption of Calmagite at 526 nm versus time using the system
2
2
O .
coordinated zinc porphyrins does not inuence the oxidation
and reduction potential of the porphyrin ring. However, the CV
curve for complex 3 exhibits a third anodic wave at ca. 1.43 V,
which is close to that previously reported [Zn(TPP)X]–ion
3
ꢀ
ꢀ
ꢀ
ꢀ
15
complexes (X ¼ N , NCO , NCS and CN ). The zinc–
porphyrin HOMO–LUMO gap can be expressed as the potential
53
difference of the rst oxidation and the rst reduction. The
estimated values of the energy gap are of 2.12 eV for 3. This
value is close to the usual value of 2.25 ꢃ 0.15 eV for metal-
54
loporphyrins. Notably, the value of the electrochemical gap Eg-
el (2.12 eV) is considerably higher than the optical gap Eg-op
Fig. 14 Evolution of the qt as a function of time using complex 1 and 3 (1.97 eV).
ꢀ
1
(m ¼ 3 mg, pH ¼ 6, C
0
¼ 30 mg L ).
3.6. Catalytic degradation of Calmagite
0
coordination of the 4,4 -bpy leading to complex 3 does not affect In this section, the adsorption and the catalytic degradation
the oxidation and the reduction potentials compared with the properties of the synthesized complexes were studied using
starting materials [Zn(TEBOP)] (Table S5†). This is also the case Calmagite as a model of an organic dye, both in the presence of
for other zinc-porphyrin derivatives [Zn(Porph)(L)] (Porph ¼ and without H
2 2 t 0
O . Fig. 13a depicts the change in the C /C value
TPP, TMP and L ¼ imidazole and 2-methylimidazole). There- of Calmagite using different combinations. Fig. 13b shows an
fore, it seems that an additional coordination of the tetra- example of the absorption spectrum of Calmagite with respect
to the time for the complex 3 combined with H O .
2
2
Fig. 15 A sort of interaction between (a): complex 1 and Calmagite (b): complex 3 and Calmagite
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Fig. 16 Kinetic data linearized through (a) pseudo first order, (b) pseudo second order (c) Elovich and (d) intra-particular diffusion equations.
¼ 30 mg Lꢀ , pH ¼ 6, m ¼ 3 mg)
1
Table 4 Kinetic parameters for the adsorption of Calmagite using complex 1 and 3 as adsorbents (C
0
Intra-particular
diffusion
Equations
Pseudo rst-order
Pseudo second-order
Elovich
2
2
2
2
Parameters
Complex 1
Complex 3
K
0.009
0.009
1
q
6.66
3.85
e
R
K
0.012
0.02
2
q
3.33
2.22
e
R
a
b
R
K
0.206
0.138
1
R
0.79
0.73
0.95
0.94
6.10
2.24
1.13
1.92
0.93
0.83
0.98
0.96
The dye solution is stable in the presence of H
2 2 2 2
O alone without the use of the oxidant agent (H O ). Under these
without the addition of any product. The trends were also experimental conditions, the adsorption capacities for the two
ꢀ
1
observed in our previous works when studying the degradation studied complexes are determined to be 3.27 mg g
and
ꢀ
1
of textile dyes using chitosan-supported [bis(2-methylallyl)(1,5- 2.25 mg g for complex 1 and complex 3, respectively (Fig. 14).
5
5
56
cyclooctadienne)ruthenium(II)], chitosan-H
3
PMo12
O
40
,
using
This slight difference in the capacity of dye adsorption
and when using oxa- means that the nitrogen active sites of the complex were
zoline complexes. The addition of the synthesized compounds engaged with the zinc metal in the second case, according to the
in the dye solution leads to the decrease of the optical absorp- proposed Fig. 15.
57,58
helically chiral metallated complexes
59
tion. These results conrm that the prepared complexes could
To understand the adsorption process of Calmagite using
be used as either an adsorbent or a catalyst. Indeed, it was seen compounds 1 and 3, data are correlated to theoretical kinetic
that the complex 1 alone, could interact with Calmagite dye via equations; pseudo rst order (Fig. 16a), pseudo second order
the adsorption process and that the adsorbed amount increases (Fig. 16b), Elovich (Fig. 16c) and intra-particular diffusion
ꢀ
1
with the evolution of time. For a dye concentration of 30 mg L
,
(Fig. 16d). Their linear forms were detailed in our previous
60–63
pH ¼ 6 and aer 240 min of reaction, the yield value of decol- work.
ourisation is about 17%. This interaction occurs through the
Results gleaned from the modeling data for Calmagite were
presence of both nitrogen and oxygen atoms and hydroxyl tabulated in Table 4. The assessment of the kinetic models is
2
groups present on the surface of the porphyrin and the organic checked by the extent of the regression coefficient R values. As
dye molecule, respectively. This yield of decolourisation is generally known, the adsorption process remains complex and
about 13% when the complex 3 is added to the dye solution there is a combination of adsorption both on the surface and
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0
1
bpy complex [Zn(TEBOP(4,4 -bpy)] (3) were synthesized. The H
NMR data reveal that the complex 3 exists as ve-coordinated
Zn-porphyrin species. The binding behaviour of the metal-
lated porphyrin [Zn(TEBOP)] with 4,4-bpy was monitored using
the absorption spectra which revealed a 1 : 1 binding stoichi-
ometry. The association constants (Kas) value of the zinc bpy-
TEBOP derivative is the smallest compared to the related zin-
c(II) meso-porphyrin with a neutral N-bond neutral axial ligand
which could be explained by their important donor character.
The photophysical experiments show that, (i) the values of lmax
Fig. 17 Linearized data for the system complex 3/H
degradation of Calmagite.
2
O
2
for the of the Q(0,0) and the Q(0,1) bands of the [Zn(TEBOP)] and
mꢃ
complex 3, as well as the reported [Zn(Porph)(L)]
(Porph ¼
meso-porphyrin and L ¼ neutral or anionic monodentate
ligand) are practically the same, (ii) the UV/Vis and uorescence
0
inside the pores. Indeed, the pseudo-rst-order equation is spectrum of 3 is not affected by the nature of the 4,4 -bipyridin
generally applicable to the initial stage of the adsorption axial ligand, while the uorescence quantum yield value
processes (Fig. 16a) and it does not t well with the range of depends on the nature of the graed group at the meso position
64
contact time in the adsorption experiments. The intra-particle of the porphyrinic ring and (iii) the singlet excited state lifetime
diffusion model is, also, used to identify the mechanism
is short, which could be explained by the relatively important
s
f
involved in the adsorption process. This model assumes that exibility of the ethyl butanoate group in para position of the
intra-particle diffusion is the rate-controlling step, which is phenyls of the TEBOP porphyrinato. The cyclic voltammogram
6
5
0
generally the case for well-mixed solutions. The applicability of our 4,4 -bipyridin-zinc(II) derivative presents two reversible
1
/2
of this model requires that the plot of qt versus t should be oxidation and reduction waves with each one attributed to
linear; if it passes through intra-particle diffusion as the only a one-electron transfer involving the porphyrin monocycle. One
66,67
rate controlling step.
Herein, the straight lines of kinetic third oxidation wave was also observed. The values of the optical
data for the intra-particular-diffusion equation pass from the and electrochemical gap are close to 2.00 eV. This could suggest
origin (Fig. 16d). This suggests that the diffusion step is the use of the prepared compound as a semi-conductor. In the
2
0
signicant in this case. Referred to as the R values of this solid state, Zn atom is penta-coordinated with the 4,4 -bpy as an
equation, this model is more suitable to describe the experi- axial ligand. The porphyrin core of 3 presents a moderate
mental data than the other equations.
ruffling distortion. The crystal packing of 3 is stabilized by weak
More importantly, as the time increases the maximum C–H/p intermolecular interactions involving the pyridyl,
absorption at 526 nm decreases gradually. In fact, the addition phenyl and pyrrole centroid rings. The prepared catalyst shows
of H O to the Zn particles provides more active sites for the a high efficiency toward the catalytic degradation of Calmagite
2
2
Calmagite improving degradation phenomenon. Under the in the presence of an ecological oxidant (H
O
) under the
2
1
2
ꢀ
studied experimental conditions mentioned above, results conditions: 3 mg of catalyst, H
reveal that about 31% of the Calmagite was degraded aer this 30 mg L and time ¼ 240 min).
O
¼ 4 mL L , pH ¼ 6, C
¼
2
2
0
ꢀ
1
time for the reaction in the presence of complex 3–H . To
2 2
O
understand the reaction kinetics of the dye degradation, the
pseudo-rst-order rate constant k was determined using the
equation:
Conflicts of interest
There are no conicts to declare.
ln C /C ¼ ꢀk t
(1)
t
0
0
Acknowledgements
where t is the time taken during the degradation, k is the rst-
order rate constant of the reaction, and C and C are the
concentrations of Calmagite dye at times t and 0, respectively.
The curve tting of the pseudo-kinetic equation is shown in
Fig. 17 according to the Langmuir Hinshelwood kinetic equa-
tion. It was, therefore, easy to deduce the rate constant of the
The present work was partially supported by Labex Arcane,
France (ANR-11-LABX-0003-01). The chemistry platform Nano-
Bio campus in Grenoble is acknowledged for luminescence
lifetime measurement facilities. T. A. Saleh would like to
acknowledge King Fahd University of Petroleum & Minerals
t
0
(KFUPM), Project No. IN161011 under the Deanship of
degradation (K
0
)
and it was found to be equal to
Research.
ꢀ
1
67–69
0.001 min .
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. Conclusion
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