Synthesis, molecular structure, spectroscopic characterization and antibacterial activity of the pyrazine magnesium porphyrin coordination polymer

Article abstract of DOI:10.1016/j.molstruc.2020.129508

A new material of magnesium(II) polymer compound with the formula {[Mg^II(TPP)(pz)]^? 0.5[Mg^II(TPP)]^?CH₂Cl₂}_n (I), (TPP) = meso?tetraphenylporphyrinato and pz = pyrazine) was synthetized and characterized by IR, UV-visible, PL photoluminescence and ¹H NMR spectroscopy studies, single-crystal XRD analyses and cyclic voltammetry. The crystal structure of (I) is made by the 1D {[Mg(TPP)(pz)]} polymeric chains (molecules I(A)) where the tetracoordinated magnesium(II) complexes [Mg(TPP)] (molecules I(B)) are located as well as the dichloromethane solvent molecules. The crystal packing of (I) is stabilized by intermolecular C[sbnd]H?Cg π interactions where Cg is the centroid of phenyl and pyrrole rings. Additionally, the photophysical properties have been evaluated by UV-visible absorption and fluorescence emission spectroscopies. The UV-visible spectrum of (I) shows a redshift Soret band value (428 nm) compared to that of the free base H₂TPP porphyrin while the λ_max values of the Q bands are in the range 560 – 610 nm. The optical gap of (I) was estimated at 1.99 eV. The cyclic voltammogram of the title compound presents two reversible oxidation waves and one reversible reduction wave. The HOMO and LUMO energy values were deduced from the voltammogram which are -4.96 and -2.85 eV respectively. Furthermore, bioactivity investigations revealed that the free porphyrin, the starting material [Mg^II(TPP)] and complex (I) could be used as potential antibacterial agents.

Full text of DOI:10.1016/j.molstruc.2020.129508

Journal Pre-proof
Synthesis, Molecular Structure, Spectroscopic Characterization and
Antibacterial Activity of the Pyrazine Magnesium Porphyrin
Coordination Polymer
Arbia Ben Khelifa , Khaireddine Ezzayani ,
Mouhieddinne Guergueb , Frederique Loiseau , Eric Saint-Aman ,
Habib Nasri
PII:
S0022-2860(20)31823-8
DOI:
Reference:
https://doi.org/10.1016/j.molstruc.2020.129508
MOLSTR 129508
To appear in:
Journal of Molecular Structure
Received date:
Revised date:
Accepted date:
13 September 2020
22 October 2020
22 October 2020
Please cite this article as: Arbia Ben Khelifa , Khaireddine Ezzayani , Mouhieddinne Guergueb ,
Frederique Loiseau , Eric Saint-Aman , Habib Nasri , Synthesis, Molecular Structure, Spectroscopic
Characterization and Antibacterial Activity of the Pyrazine Magnesium Porphyrin Coordination Poly-
mer, Journal of Molecular Structure (2020), doi: https://doi.org/10.1016/j.molstruc.2020.129508
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Highlights




Synthesis of a new Mg(II) porphyrin polymer with the pyrazine ligand: (I).
UV-visible and fluorescence spectroscopic characterization of (I).
Cyclic voltammetry investigation of (I).
X-ray molecular structure of (I) showing C-H… intermolecular interactions.

exhibits promising antibacterial activity for Gram-(+) and (-) bacteria.

Synthesis, Molecular Structure, Spectroscopic Characterization
and Antibacterial Activity of the Pyrazine Magnesium Porphyrin
Coordination Polymer
a,b
b
b
Arbia Ben Khelifa , Khaireddine Ezzayani , Mouhieddinne Guergueb , Frederique
c
c
b
Loiseau , Eric Saint-Aman and Habib Nasri .
a
b
Department of Chemistry, University College at al khafji, University of Hafr al Batin, 39256 al khafji, Saudi Arabia. Laboratoire de
Physico-chimie des Matériaux, Faculté des sciences, Avenue de l'environnement, 5019 Monastir, Université de Monastir, Tunisie.
c
ꢀꢁiꢂꢃꢄꢅiꢆꢇ ꢈꢄꢃꢁꢉꢊꢋꢃ-ꢌꢋꢍꢃꢅꢎ ꢏNꢐꢑꢎ ꢒꢇꢍꢓꢄꢆꢃꢔꢃꢁꢆ ꢕꢃ ꢏhiꢔiꢃ Mꢉꢋꢇꢖꢗꢋꢓiꢄꢃꢎ ꢘ384ꢙꢙ ꢈꢄꢃꢁꢉꢊꢋꢃꢚ France.
Abstract
II

A new material of magnesium(II) polymer compound with the formula {[Mg (TPP)(pz)]
II

0
.5[Mg (TPP)] CH Cl } (I), (TPP) = meso-tetraphenylporphyrinato and pz = pyrazine) was
2
2 n
1
synthetized and characterized by IR, UV-visible, PL photoluminescence and H NMR
spectroscopy studies, single-crystal XRD analyses and cyclic voltammetry. The crystal
structure of (I) is made by the 1D {[Mg(TPP)(pz)]} polymeric chains (molecules I(A)) where
the tetracoordinated magnesium(II) complexes [Mg(TPP)] (molecules I(B)) are located as
well as the dichloromethane solvent molecules. The crystal packing of (I) is stabilized by
intermolecular C-H⋯Cg π interactions where Cg is the centroid of phenyl and pyrrole rings.
Additionally, the photophysical properties have been evaluated by UV-visible absorption and
fluorescence emission spectroscopies. The UV-visible spectrum of (I) shows a redshift Soret
band value (428 nm) compared to that of the free base H TPP porphyrin while the max values
2
of the Q bands are in the range 560 – 610 nm. The optical gap of (I) was estimated at 1.99 eV.
The cyclic voltammogram of the title compound presents two reversible oxidation waves and
one reversible reduction wave. The HOMO and LUMO energy values were deduced from the
voltammogram which are -4.96 and -2.85 eV respectively. Furthermore, bioactivity
II
investigations revealed that the free porphyrin, the starting material [Mg (TPP)] and complex
(
I) could be used as potential antibacterial agents.
KEYWORDS: Magnesium porphyrin complexes, Coordination polymer, X-ray molecular
structure, cyclic voltammetry, Antibacterial agents.
Introduction
Porphyrins are naturally occurring species such as the protoporphyrin IX presents in hemes, in
cytochromes P450 and in chlorophylls. Porphyrins and metalloporphyrins have very
interesting physicochemical properties (UV-visible, fluorescence, redox, etc.) which make
them particularly attractive in a large number of areas.[1–4] These fields of application
require more complex molecular architectures and more elaborate porphyrinic nucleus
substitution schemes. And seeing that porphyrinic units are remarkable precursors in
supramolecular chemistry as excellent components in the design of efficient molecular
materials with improved electrochemical and photo-physical properties.[5] Indeed, these
porphyrinic macrocycles are used in several projects, such as photo-induced electron transfer
[
6,7], semiconductors [8], chemical sensors [9], and photovoltaic solar cells.[10] Recently
studies have shown that porphyrins are also effective against viruses and yeasts.[11,12]
Likewise, the porphyrin nucleus presents an efficient source for the synthesis of a large
number of active antimicrobial and antioxidant agents.[13–15] In addition, several porphyrin
compounds have been developed as photosensitizers for photodynamic therapy.[16,17]
During the last decades, many crystal structures of porphyrins and metalloporphyrins have

been reported whose physicochemical properties and crystal stacking are governed by axial
ligands coordination modes.[18] Furthermore, much effort has been directed toward the
creation of organized self-assemblies that result in microporous crystalline solids based on
meso-tetraarylmetalloportphyrins.[19,20] These species are known as building blocks, which
have interesting applications.[21] Among M(II) porphyrins, magnesium(II) porphyrins are
the least studied compounds. Our research group has extensive experience in the design and
characterization of new materials based on metalloporphyrins with several metals such as
iron, cobalt, cadmium, manganese and magnesium. [22-26] Notably, the increasing number of
polymers based on metalloporphyrins [27] where different synthetic methods are employed to
obtain such type of polymers. One of these methods adopts the central metal coordination
strategy of a metalloporphyrin through the nitrogen atoms of a bidentate ligand.[28] The
present work is a continuation of our investigation on magnesium (II) metalloporphyrins
[
26,29-30] where the pyrazine meso-tetraphenylporphyrin magnesium(II) coordination
complex (complex (I)) is synthesized and characterized by single crystal X-ray diffraction.
The UV-visible, fluorescence, cyclic voltammetry investigations of the complex (I) are
reported. The antibacterial activity of our Mg(II) porphyrin compounds were tested against
some Gram (+) (Staphylococcus aureus, Enterococcus faecalis) and Gram (-) (Pseudomonas
aeruginosa and Escherichia coli) bacteria.
Experimental section
Materials and methods
All chemicals/reagents used were of analytical grade and were used as received without any
ꢍꢗꢄifiꢖꢓꢆiꢉꢁꢚ Thꢃ ꢕiꢖhꢋꢉꢄꢉꢔꢃꢆhꢓꢁꢃ (DCM), hexane, magnesium chloride (MgCl2),
dimethylformamide (DMF), pyrrole, pyrazine, propionic acid, ethanol and benzaldehyde were
purchased from Sigma-Aldrich. The meso-tetraphenylporphyrin (H TPP) and the (meso-
2
tetraphenylporphyrinato)- magnesium(II) ([Mg(TPP)], was synthesized according to the
reported methods. Electronic absorption spectra were taken in a SPECORD 200 (analytikjena)
UV-Visible spectrophotometer. Luminescence properties of the complexes were analyzed
1
using an Horiba Scientific Fluoromax-4 Fluorescence spectrophotometer. IR. And H NMR
spectra were obtained using, successively, a Shimadzu FTIR-8400 spectrophotometer in the
-1
4
000–400 cm range and a Bruker 300 MHz Spectrometer. For single crystal X-ray
ꢕiffꢄꢓꢖꢆiꢉꢁ ꢅꢆꢗꢕiꢃꢅꢎ ꢆhꢃ ꢕiffꢄꢓꢖꢆꢃꢕ ꢖꢄyꢅꢆꢓꢋ wꢓꢅ gꢋꢗꢃꢕ ꢆꢉ ꢓ gꢋꢓꢅꢅ fiꢊꢄꢃ ꢓꢁꢕ ꢔꢉꢗꢁꢆꢃꢕ ꢉꢁ Bꢄꢗkꢃꢄ
XSCANS diffractometer. The instrument has CCD area detector and data intensity has been
collected at 153 K using graphite-ꢔꢉꢁꢉꢖhꢄꢉꢔꢓꢆꢃꢕ Mꢉ Kα ꢄꢓꢕiꢓꢆiꢉꢁ (λ= ꢙꢚ71ꢙ73 Å)ꢚ Thꢃ ꢗꢁiꢆ-
cell parameters were calculated and refined from the full data set. The reflections were scaled
and corrected for absorption effects by using SADABS. [31] The structure is solved by direct
methods using SIR-2004 program [31] and refined using the SHELXL-2015 program.[32]
The hydrogen atoms were placed in calculated positions and refined by using a riding model.
The crystallographic data and structural refinement details of (I) is shown in Table 1. The
electrochemical measurements were performed in an electrochemical workstation CH
instrument CHI600E using glassy carbon electrode as the working electrode, Pt electrode as
an auxiliary electrode and Ag/AgCl electrode as a reference electrode.
Synthesis
Synthesis of the meso-tetraphenylporphyrin (H TPP)
2
The meso-tetraphenylporphyrin (H TPP) was synthesized from the acid catalyzed
2
condensation of pyrolle (4 mol eq.) and benzaldehyde (4 mol eq.) in the presence of propionic
acid.[33] Benzaldehyde (1.62 mL, 16 mmol) and pyrrole (1.11 mL, 16 mmol) were combined

ꢓꢁꢕ hꢃꢓꢆꢃꢕ ꢗꢁꢕꢃꢄ ꢄꢃflꢗx fꢉꢄ 1 h iꢁ ꢆhꢃ ꢍꢄꢃꢅꢃꢁꢖꢃ ꢉf ꢍꢄꢉꢍiꢉꢁiꢖ ꢓꢖiꢕ (1ꢙꢙ ꢔL)ꢚ Thꢃ ꢍꢄꢉꢕꢗꢖꢆ wꢓꢅ
fiꢋꢆꢃꢄꢃꢕ ꢉffꢎ ꢆhꢃꢁ wꢓꢅhꢃꢕ wiꢆh hꢉꢆ wꢓꢆꢃꢄ ꢓꢁꢕ ꢔꢃꢆhꢓꢁꢉꢋ ꢗꢁꢆiꢋ ꢆhꢃ fiꢋꢆꢄꢓꢆꢃ wꢓꢅ ꢖꢉꢋꢉꢄꢋꢃꢅꢅꢎ ꢓffording
purple glistering crystals.
II
Synthesis of the (meso-tetraphenylporphyrinato)magnesium(II) complex [(Mg (TPP)]
A sample of 1 g (1.02 mmol) H TPP and 0.554 g (4.07 mmol) of magnesium chloride was
2
ꢄꢃflꢗxꢃꢕ iꢁ 12ꢙ ꢔL ꢒMꢘ fꢉꢄ 6 hꢚ ꢌfꢆꢃꢄ ꢄꢃꢔꢉꢂiꢁg ꢆhꢃ solvent, the solid product was dissolved
in dichloromethane (DCM)ꢎ fiꢋꢆꢃꢄꢃꢕ ꢓꢁꢕ ꢕꢄiꢃꢕ under vacuum.[34] The crystals ware obtained
from a mixture of dichloromethane-ethanol-hexane solvent.
Synthesis of complex the catena-poly{(pyrazine)(meso-tetraphenylporphyrinato)
magnesium(II)}(meso-tetraphenylpor-phyrinato)magnesium(II) dichloromethane
monosolvate
II
[
Mg (TPP)] (15 mg, 0.023 mmol) was dissolved in 5 mL of distilled dichloromethane.
Pyrazine (15 mg, 0.09 mmol) was then added and the solution was stirred at room
temperature for 10 hours. Crystals of the title complex (I) were obtained by slow diffusion of
n-hexane through the dichloromethane solution. Anal. Calcd (found) for C H N Mg2.25Cl4
142 96 16
(
2222.84 g/mol): C, 76.94; H, 4.36; N, 10.11%. Found: C, 76.80; H, 4.25; N, 10.05%. UV–
-1
vis [CH Cl : λ
2
in nm (log)]: 428 (5.96), 568 (4.60), 608 (4.35). IR (solid, cm ): 3000-
2
2
max
1
850, 932-536, 998, 1240, 1506, 1463, 1355, 1132, 1585, 2950, 2843. H NMR (300 MHz,
CDCl , 298 K):  8.85 ppm (s, 8 H, pyrrole ß-H), 8.15 ppm (dd, 8 H, (J= 8.2, 7.8 Hz), TPP
3
o-H), 7.62-7.83 ppm (m, 12 H, TPP m-, p-H), 6.34 ppm (dd, 4 H, (J=8.6, 4.8 Hz pyrazine).
Table 1. Crystal parameters of compound (I).
_
___________________________________________________________________________________________________________
Chemical formula
C142H N Mg2.25Cl4
2222.84
0.45 × 0.39 × 0.36
Triclinic
P-1
13.189 (3)
14.877 (3)
15.996 (3)
110.48 (3)
102.32 (3)
92.18 (3)
2850.6 (12)
2
96
16
-
1
Formula Weight M (g.mol )
r
3
Crystal size/mm
Crystal System
Space Group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V(Å )
3
Z
Reflections collected
33620
Independent / observed reflections 11018, 8060
Rint
dcalc./ g cm
μ/ mm
0.047
1.29
0.179
-
3
-
1
T(K)
293(2)
1155
0.063, 0.209
1.04
F(000)
a
b
R , wR2
1
GooF (S)
3
∆
(max, min) (e/Å ) 0.98, −0.47
ρ
_
a
_______________________________________________________________________________________________
:
R
= Σ||F | – |F ||/Σ|F |.
1 o c o
b
2
2 2
2 2 1/2
:
wR = {Σ
[w
(|F |
o
–
|F |
c
)
]/
Σ
[
w )
(|F |
]}
.
2
o
Antibacterial screening

Pathogenic strains were cultivated on nutrient agar at 37 °C for 24 h. Then, pure colonies
were suspended in 10 mL of physiological medium, mixed during 5 min and suspensions
were adjusted to 0.5 McFarland standard turbidity. The milliliter of bacterial suspension was
spread over Muller Hinton Agar medium plates and incubated for 30 min at 37 °C. Then, 6
mm diameters wells were dug in agar medium using sterile glassy borer. The Mg(II)
complexes were dissolved in DMSO (1 mg/mL) and were introduced into the respective
-5
wells, leading to a final concentration of 10 M, one of the wells was supplemented with
DMSO as control. These plates were placed in a 37 °C incubator for 24 h to allow bacterial
growth. After 24 h, the diameters of the clear zone of inhibition surrounding the sample were
measured in millimeters by digital caliper.
Results and discussion
Spectroscopic studies
UV-vis absorption spectroscopy
The electronic spectra of porphyrins and metalloporphyrins manifest high sensitivity toward
structural modifications. Figure 1 shows the UV-visible absorption spectra in
II
dichloromethane solvent of the free-base porphyrin H TPP, [Mg (TPP)] starting material and
2
complex (I). The absorption spectra of the free bae porphyrin consists of one strong B band,
known as the Soret band, in the near UV region located at 420 nm followed by four weaker Q
bands in the visible region between 500 and 700 nm. The starting material display one higher
intensity Soret band located at 425 nm followed by two lower intensity Q bands between 500
and 700 nm. The Soret and Q bands are assigned to S  S and S  S (π-π*) transitions
0
2
0
1
within the highly π conjugated macro-rings. it is noted that the number of Q bands reduced for
the metallic porphyrins is due to the increase in symmetry (from D2h to D ). The lower
4h
symmetry (D ) of free base porphyrin is ascribed to the presence of two diagonally
2
h
positioned hydrogen atoms in its N4 core [35]. The coordination of magnesium(II) ion with
the ligand (pyrazine) induces bathochromic shift of the Soret and the Q bands as illustrated by
Figure 1. This phenomenon is usually attributed to the porphyrinic ring deformation due to
coordination of magnesium(II) ion.
II
Figure 1. UV-visible absorption spectra of H TPP, Mg (TPP), and compound (I),
2
-
6
-1
in dichloromethane solution at concentrations around 10 mol.L .

The energy difference between the levels of the HOMO and LUMO (optical band gap) [36] is
obtained from the UV-visible spectrum. The optical gap energy (Eg-op) is calculated from the
Tauc plot method as shown in Figure 2. The Eg-op value of (I) is 1.99 eV, which is in the
normal range of meso-arylporphyrins and meso-metalloporphyrin. This is an indication that
complex (I) exhibits semiconductor properties.
2
II
Figure 2ꢚ Pꢋꢉꢆꢅ ꢉf (αhυ) versus the photon energy (E) of H TPP, [Mg (TPP)] and compound (I),
2
α iꢅ ꢆhꢃ ꢓꢊꢅꢉꢄꢍꢆiꢉꢁ ꢖꢉꢃfficient.
II
Table 2. UV-visible data of H TPP, the starting material [Mg (TPP)], compound (I) and a selection of related
2
compounds.
_
_______________________________________________________________________________________________________________________________________________
Compound
Soret band (nm)
logε)
Q bands (nm)
(logε)
Eg-op. [ref]
(eV)
(
_
_______________________________________________________________________________________________________________________________________________
a
H TPP
418 (6.92) 515 (5.73) 550(4.33) 588(4.42) 648(4.20)
416 (6.10) 513 (5.70) 550(4.36) 590(4.24) 646(4.19)
1.86
1.86
1.83
2.00
-
t.w.
2
H TPP
[37]
[38]
t.w.
[39]
t.w.
[26]
[40]
2
H TPP
-
-
-
-
-
2
II
[
[
Mg (TPP)]
Mg(TPP)]
425 (5.97)
424 (5.87)
428 (5.96)
564 (4.70)
563 (4.52)
568(4.60)
575 (4.97)
564 (4.25)
604 (4.48)
603 (4.39)
608(4.35)
617 (4.98)
604 (3.95)
Complex (I)
1.99
1.96
-
b
[
[
Mg(TPP)(HMTA) ] (II) 434 (6.22)
2
Mg(TPP)(THF) ]
426 (5.75)
2
_
________________________________________________________________________________________________________________________________________________
a
b
:
t.w.: this work, : HMTA = hexamethylenetetramine.
Steady-state emission spectroscopy
Luminescence properties of compound (I) was studied at room temperature in
dichloromethane solution. The spectrum of (I) exhibits ꢆwꢉ wꢃꢋꢋ ꢕꢃfiꢁꢃꢕ flꢗꢉꢄꢃꢅꢖꢃꢁꢖꢃ ꢍꢃꢓkꢅ
at 616 and 670 nm (Figure 3) assigned as Q(0,1) and Q(0,0) respectively, upon in the
excitation of 617 nm. The luminescence quantum yields of the synthesized compounds are
calculated by the approach of relative method of measurement [41], in which the integrated
luminescence intensities are measured using magnesium porphyrin complex [Mg(TPP)] as the
standard (= 0.15). Wꢃ ꢔꢃꢓꢅꢗꢄꢃꢕ ꢆhꢃ flꢗꢉꢄꢃꢅꢖꢃꢁꢆ ꢋifꢃꢆiꢔꢃ (τ ) in dichloromethane solution, By
f
means of a time-correlated single photon counting technique. The photoluminescent lifetime

of compound (I) is 4.5 ns. The fluorescence wavelengths of the fluorescence bands, the
fluorescence quantum yields (ɸ )ꢎ ꢓꢁꢕ ꢆhꢃ fꢋꢗꢉꢄꢃꢅꢖꢃꢁꢖꢃ ꢋifꢃꢆiꢔꢃꢅ (τ ) values of the starting
f
f
II
material [Mg (TPP)], complex (I) and some related porphyrin species are summarized in
Table 3.
II
Figure 3. Emission spectra of H TPP, [Mg (TPP)] and compound (I)
2
-
6
-1
in dichloromethane solution at 10 mol.L concentration.
II
Table 3. Emission characteristics of H TPP, [Mg (TPP)], complex (I) and a selection of other magnesium
2
mesotetraporphyrins compounds.
_
_____________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________
Compound
Q(0,0) [nm]
Q(0,1) [nm]
ϕ
τ [ns]
ref.
f f
_
_____________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________
a
H TPP
650
653
608
608
616
713
722
663
661
670
665
660
0.11
0.12
0.13
0.15
0.12
0.14
0.16
8.0
9.6
5.0
9.2
4.5
4.7
8.9
t.w.
2
H TPP
[42]
t.w.
[43]
t.w.
[26]
[44]
2
II
[
[
Mg (TPP)]
Mg (TPP)]
II
Complex (I)
b
[
[
Mg(TPP)(HMTA) ] (II) 620
2
Mg(TPP)(THF) ]
609
2
_
_____________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________
a
b
:
t.w. = This work, : HMTA = Hexamethylenetetramine.
Cyclic voltammetry investigation
We have studied the electrochemistry properties of our Mg-TPP-pz derivative using the cyclic
voltammetry technique. This investigation was in DCM using tetrabutylammonium
perchlorate (TBAP) as supporting electrolyte (0.2 M). As shown in Figure 4, our synthesized
compound (I) exhibits two reversible oxidation waves and one reversible reduction wave.
These oxidation and reduction waves are attributed to the porphyrin macrocycle.

Figure 4. Cyclic voltammogram of complex (I).The solvent
is CH2Cl2,and the concentration is ca. 10-3 M in 0.2 M TBAP,
5
0 mV/s, vitreous carbon working electrode (Ø = 3 mm).
Figure 4 illustrates the cyclic voltammogram of the compound (I). The two first successive
anodic waves (O1/R1) and (O2/R2) are reversible and correspond to one-electron transfers
involving the porphyrin cores. The correspondent potential values of these waves are 0.34 V /
0
.59 V. In the negative potential region, the cyclic voltammograms of (I) exhibits reversible
one-electron porphyrin-ring-centered cathodic waves (O3/R3) at E (1/2) at ca. –1.78 V. In
d
that way, the response of (I) is representative of the classical behavior of metalloporphyrins
with a no electroactive metal (such as Zn Mg and Cd), which undergoes two reversible one
electron transfers, both in oxidation and reduction. For (I), the second reduction of the
porphyrin is not observed since it falls beyond the solvent reduction. A summary of the half-
wave potentials of porphyrin ligands and Mg complexes is listed in Table 4.
From the voltammogram of (I) we determined the HOMO and LUMO energy levels and the
electrochemical gap (Eg-el) can be calculated by the following relations [45]:
EHOMO (IP: ionization potential) = - (Vonset-ox – V + 4.8 ) eV
ref
ELUMO (EA: electron affinity) = - (Vonset-red – Vref + 4.8 ) eV
Eg-el = (ELUMO – E HOMO) eV
where Vonset-red is the reduction onset, Vonset-ox is the oxidation onset and V is the ferrocene
ref
+
half-wave potential (0.42 V). The energy level of the Fc /Fc is assumed to be 4.8 eV below
the vacuum level.
Table 4. Redox potential data (in V) for the H TPP porphyrin, complex (I) and a selection of magnesium
2
metalloporphyrins compound. All data are obtained from voltammograms recorded in dichloromethane and the
potentials are reported versus SCE.
_
___________________________________________________________________________________________________________________________________________________________________________________
Compound
Oxidation Reduction
Ref.
-
------------------- ------------------
Eonset-ox Eonset-red EHOMO ELUMO Eg-el
O1/R1 O2/R2
O3/R3 O4/R4
_
___________________________________________________________________________________________________________________________________________________________________________________
a
H TPP
1.07 1.31 -1.47 -1.15
0.65 -1.36 -5.50 -3.49 2.01 [46]
0.23 -1.61 -4.88 -3.04 1.84 [26]
2
II
b
[
[
[
Mg (TPP)]
Mg (TPP)(THF) ]
Mg (TPP)(HMTA) ] 0.73 0.99 -1.45 -
0.34 0.59 -1.92 -
0.65 0.94 -1.57 -
II
-
-
-
-
2.22 [44]
2
II
c
0.57 -1.33 -4.93 -3.03 1.90 [26]
2
d
Complex (I)
0.65 0.95 -1.65 -
0.58 -1.53 -4.96 -2.85 2.11 t.w.
_
__________________________________________________________________________________________________________________________________________________________________________________
a
b
c
d
:
0.1 M NBu PF
4 6
in CH
3
CN; : 0.2 M TBAP in CH
Cl
2 2
; : HMTA = Hexamethylenetetramine; : t.w.: this work,.

X-ray diffraction
Crystal of (I) suitable for X-ray diffraction study were obtained by slow diffusion of n-hexane
through the DCM solution containing complex (I). Complex (I) crystallizes in a triclinic
system with the space group P-1. The crystallographic data and the structural refinement
details are reported in Table 1. The single crystal X-ray diffraction study shows that in the
crystal lattice of complex (I) two types of molecules are presents. Indeed, a one dimensional
chain made by [Mg(TPP)(pz)] monomer (molecule IA) coexists with the tetracoordinated
[
Mg(TPP)] complex (molecule IB) and a dichloromethane solvent molecule. This means that
the asymmetric unit of (I) is by one [Mg(TPP)(pz)] moiety, a half [Mg(TPP)] molecule and
one DCM solvent molecule. The ORTEP diagrams of the crystallographically independent
molecules (A and B) and the dichmoroethane molecule of (I) are shown in Figure 5.
Figure 5. ORTEP diagram of complex (I). The hydrogen atoms are omitted for clarity and thermal
ellipsoids are drawn at the 50% probability level.
The coordination sphere of Mg(II) cation for molecule IA is described as octahedron, in
which equatorial positions are occupied by the four pyrrole nitrogen atoms and the apical
positions are occupied by N-donor atoms of the pyrazine molecules. Structural arrangement
along the a-axis is shown in Figure 6.

Figure 6. Representation of the 1D Mg-porphyrin chains (molecules IA) and molecules IB.
The framework of (I) consists of a 1D polymer chain extending along the (a) axis in which the
magnesium centers are bridged by pyrazine ligands, forming a Mg-pyrazine-Mg linear
polymer. This chain is twisted to minimize the steric hindrance due to the presence of the
[
Mg(TPP)] (molecules IB) and the DCM solvent molecules between these chains. Figure 7 is
an illustration of the crystal packing of (I).
Figure 7. Representation of the crystal packing of (I).
The values of the mean equatorial distance between the central metal and the four nitrogens of
_
_
the porphyrin (Mg Np) are respectively 2.072 (2) Å and 2.112 (2) Å for (IA) and (IB). The
Mg__Np of the {[Mg(TPP)(pz)]} coordination polymer b(molecule IA) is very close to those
of the related hexacoordinated Mg(II) metalloporphyrins (Table 5) which is not the case of the
_
_
[
Mg(TPP)] complex (molecule IB). For this later species, the Mg Np is quite high (2.112 (2)
Å) which is due to the disordered Mg atom located in the inversion center.
In the molecule (IA), the magnesium-nitrogen bond length value of the axial ligand
_
_
(
Mg N(pz) is 2.341 (2) Å. This value is comparable to those of related Mg(II)-porphyrins

with N-ꢕꢉꢁꢉꢄ ꢖyꢖꢋiꢖ ꢓxiꢓꢋ ꢋigꢓꢁꢕ ꢅꢗꢖh ꢓꢅ 4ꢎ4’-bipyridine, 4-picoline, piperazine and pyridine
Table 5).
(
Table 5. Selected bond lengths in several hexacoordinate magnesium metalloporphyrins.
_
_____________________________________________________________________________
a
b
Compound
Mg—N (Å)
Mg—N (Å)
ref
L
p
_
_____________________________________________________________________________
Molecule (IA)
2.341(2)
2.068(2)
t.w.
t.w.
t.w.
[47]
[48]
[49]
[50]
[51]
[51]
[51]
[52]
[53]
[53]
2
.077(2)
Molecule (IB)
----------
2.259(3)
2.121(2)
2.319-2.290
2.3764(2)
2.297(8)
2.386(2)
2.419(4)
2.369(2)
2.259(3)
2.112(2)
2.087(2)
2.095(2)
2.065
2.071(5)
2.078(10)
2.071(4)
2.072(5)
2.063(3)
2.087(2)
2.100(2)
c
[
[
[
Mg(tn-OEP)(4ꢎ4’-bpy)]
Mg(TBrPP)(HIm)]
Mg(TPBP)(4,4′-bpy)2]f
d,e
[
[
[
[
[
[
Mg(TPP)(py)2]
Mg(TPP)(1-MeIm) ]
Mg(TPP)(4-pic) ]
Mg(TPP)(pip)2]
g
2
h
2
i
Mg(TPP)(py) ]
2
II
Mg (OEP) (4ꢚ4’-dipy) ]
2
2
2
.272(3)
_
_______________________________________________________________________________
a
b
:
L p
Mg—N = distance between the metal and the nitrogen of the N-donor axial ligand, : Mg—N = average equatorial metal–nitrogen
c d e f
pyrrole distance, : tn-OEP = octaethyl-tetranitroporphyrinato, : TBrPP = meso-bromophenyl)porphyrinato, : Him = imidazole, : TPBP
meso-tetrabenzoyloxyphenylporphyrinato, : 1-MeIm = 1-methylmidazole, : 4-pic = 4-picoline, : pip = piperidine.
g
h
i
The coordinating compound (I) consists of one-dimensional polymeric chains along axis a
(
(
molecule IA). These chains define cavities containing the Mg(II) porphyrin complexes
molecule IB) (Figure 7). The two planes containing the porphyrin macrocycles of one
Mg(TPP)-py-Mg(TPP) dimer of the polymer (molecules IA) presents a angle value equal to
1 ° (Figure 8) This tilte is fore probably due, as was already mentioned, to the presence of
2
the [Mg(TPP) (molecules IB) and the DCM solvents molecules. The crystal lattice of (I) is
stabilized by intermolecular interactions type C-H···Cg where Cg is the center of gravity of
the nucleus (centroid) of a pyrrole or a phenyl ring (Figure 9). The intra molecular and the
intermolecular distances C-H···Cg are summarized in Table 6.
Table 6. Intermolecular and intramolecular interactions for complex (I).
_
____________________________________________________________________
a
D – H···A
Symmetry of A
D···A (Å)
D – H···A (°)
_
____________________________________________________________________
C12A–H12A···Cg2
C14A–H14A···Cg11
C15A–H15A···Cg4
C19A–H19A···Cg1
C22–H22···Cg5
C23–H23···Cg1
C25–H25···Cg3
C48–H48···Cg5
x,y,z
-1+x,y,z
1-x,-y,1-z
2-x,1-y,1-z
x,y,z
x,y,z
x,y,z
1-x,-y,1-z
3,750(3)
3,858(3)
3,468(4)
3,592(5)
3,318(4)
3,445(3)
3,739(3)
3,840(4)
142
160
138
161
107
129
143
159
_
____________________________________________________________________
a
:
D = donor atom and A= accepter atom.
Cg1 is the centroid of the N1-C1-C2-C3-C4 pyrrole five membered ring.
Cg2 is the centroid of the N2-C6-C7-C8-C9 pyrrole five membered ring.
Cg3 is the centroid of the N6-C27-C28-C29-C30 pyrrole five membered ring.
Cg4 is the centroid of the N7-C32-C33-C34-C35 pyrrole five membered ring.
Cg5 is the centroid of the N8A-C1A-C2A-C3A-C4A pyrrole five membered ring.
Cg11 is the centroid of the C17A-C18A-C19A-C20A-C21A-C22A phenyl six membered ring.

Figure 8. Drawing showing the angle between the two planes of the two successive
porphyrins that constitute the polymer (IA).
Figure 9. Schematic representation of the intermolecular C–H···ꢏgꢎ π iꢁꢆꢃꢄꢓꢖꢆiꢉꢁꢅꢚ
Antibacterial activity
Porphyrins appeal large attention because of their significant antibacterial activity.[54-58] In
the present work, we evaluated the antibacterial activity of the free base porphyrin H TPP, the
2
starting material [Mg(TPP)] and complex (I) which were tested at the concentration of 100
휇g/mL against two Gram-negative bacteria (Pseudomonas aeruginosa (ATCC 27853) and
Escherichia coli (ATCC35218)) and two Gram-positive bacteria (Staphylococcus aureus

(ATCC 25923) and Enterococcus faecalis (ATCC 29212)) using well agar diffusion assay as
described by Mahdhi et al. [59]
II
Figure 10. In vitro antimicrobial activity of H TPP, Mg (TPP) and compound (I).
2
Analysis of the results shows that the meso-phenylporphyrin H TPP has moderate activity
2
against E. faecalis with an inhibition zone of 11 mm and low activity against S. aureus with an
inhibition zone of 4 mm. However, this inhibition zone was not observed on the two bacteria
P. aeruginosa and E. coli. For the metallated porphyrin [Mg(TPP)] and [Mg(TPP)(pz)] After
insertion of the metal Mg(II) in(I) complexes we noticed a slight increase in the activity for E.
faecalis (13 mm) and E. coli (3 mm), and improved antibacterial activity against S. aureus
with an inhibition zone of 16 mm. Furthermore, complex (I) is the most effective against all
strains tested with the highest antibacterial activity. This pyrazine magnesium derivative
shows an inhibition zone diameter of 11 mm and 12 mm against P. aeruginosa and E. coli,
respectively. It also inhibites E. faecalis by 14 mm and S. aureus by 15 mm. These values are
higher than those obtained with the standard drug tetracycline which has ~ 12 mm diameter
inhibition zone against P. aeruginosa and E. coli. [59] If we look closely at the results we can
see that the metal insertion has an effect on the inhibition zone. The improved antimicrobial
performance of the complexes can be attributed to the Overtone's concept and Tweedy's
chelation theory. [60, 61] Chelation reduces the polarity of the metal ion, mainly because of
the partial sharing of its positive ꢖhꢓꢄgꢃ wiꢆh ꢆhꢃ ꢕꢉꢁꢉꢄ gꢄꢉꢗꢍꢅ ꢉf ꢋigꢓꢁꢕꢅ ꢓꢁꢕ ꢍꢉꢅꢅiꢊꢋy ꢆhꢃ π
electron delocalization within the whole chelate ring system thus formed during coordination.
This process of chelation thus strengthens the lipophilic character of the central atom, which
in turn favors its permeation through the lipoid layer of the membrane [62-68], and hence
enhances the biological utilization ratio and activity of the compounds. The literature survey
revealed that antibacterial activity of magnesium porphyrinic compounds are comparable.
Conclusion
In summary, we have prepared and characterized a new polymer magnesium(II) porphyrin
coordination compound (I). The UV-visible and fluorescence spectra of (I) show results

similar to those of the already known Mg(II) porphyrins, the quantum yield value and the
flꢗꢉꢄꢃꢅꢖꢃꢁꢆ ꢋifꢃꢆiꢔꢃ ꢓꢄꢃ iꢁ ꢆhꢃ ꢗꢅꢗꢓꢋ ꢄꢓꢁgꢃꢅ ꢄꢃꢍꢉꢄꢆꢃꢕ fꢉꢄ meso-
tetraphenylporphyrinato)magnesium(II) species. The cyclic voltammetry investigation on
complex (I) are also reported and the electrochemical gap values of these porphyrin species
were determined from the voltammograms which are slightly higher than those of the optical
II

gap. The X-ray investigation shows that the crystal lattice of (I) is made by {[Mg (TPP)(pz)]
II

0
.5[Mg (TPP)] CH Cl } (I), (TPP = meso-tetraphenylporphyrinato and Py = pyrazine)
2
2 n
complex aligned in one dimensional chain along to the a axis. The supramolecular structure of
I) is made by the polymer chains (molecules A), are sustained by weak C-Hꢚꢚꢚπ iꢁꢂꢉꢋꢂiꢁg ꢏg
(
pyrrole and phenyl centroids rings intermolecular interactions, with the magnesium porphyrin
molecules uncoordinated (molecules B). Furthermore, the antibacterial studies shows that
there tested porphyrin species have significant antibacterial activity and that complex (I)
exhibits a better activity and could be a promising species to design antibacterial activity
molecule against bacterial strains. Improvement to enhance activity against other strains will
be investigated.
Acknowledgement
The present work was partially supported by Labex Arcane, France (ANR-11-LABX-0003-
0
1). The chemistry platform NanoBio campus in Grenoble is acknowledged for measurement
facilities. The authors thank Christian Philouze from molecular chemistry department-
Grenoble Alpes University for the crystal mounting and data collection. The authors
gratefully acknowledge support from the University of Hafr Al Batin, Saudi Arabia and the
Ministry of Higher Education and Scientific Research of Tunisia.
Appendix A. Supplementary data
CCDC 2023484 contain the supplementary crystallographic data of complex (I). These data
can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from
the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
CRediT author statement
All persons who meet authorship criteria are listed as authors, and all authors certify that they
have participated sufficiently in the work to take public responsibility for the content,
including participation in the concept, design, analysis, writing, or revision of the manuscript.
Furthermore, the corresponding author is responsible for ensuring that the descriptions are
accurate and agreed by all authors and certifies that this material has not been and will not be
submitted to or published in any other publication before its appearance in the Journal of
Molecular Structure – Elsevier.
Authorship contributions
Arbia Ben Khelifa: Writing-eviewing and Editing, Conceptualization, Methodology,
Software.

Khaireddine Ezzayani and Mouhieddinne Guergueb: Data curation, Writing- Original draft
preparation.
Frederique Loiseau: Visualization, Investigation, Software, Validation.
Eric Saint-Aman and Habib Nasri: Supervision.
DECLARATION OF INTEREST
I declare that we as authors have a responsibility to disclose any interests that
may appear to influence the presentation of data objectively
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GRAPHICAL ABSTRACT