Synthesis, Electronic Spectroscopy, Cyclic Voltammetry, Photophysics, Electrical Properties and X-ray Molecular Structures of meso-{Tetrakis[4-(benzoyloxy)phenyl]porphyrinato}zinc(II) Complexes with Aza Ligands

Article abstract of DOI:10.1002/ejic.201600575

The synthesis of the new meso-porphyrin tetrakis[4-(benzoyloxy)phenyl]porphyrin (H₂TPBP), the meso-{tetrakis[4-(benzoyloxy)phenyl]porphyrinato}zinc(II) starting material [Zn(TPBP)] (1), and the 1,4-diazabicyclo[2.2.2]octane (dabco), pyrazine (pyz), 4,4′-bipyridine (4,4′-bpy), 4,4′-diaminodiphenylmethane (4,4′-mda), and 4-cyanopyridine (4-CNpy) coordination compounds with [Zn(TPBP)] (2–7) are described. The preparation of the dabco derivative in chlorobenzene leads to a crystalline monomeric five-coordinate zinc porphyrin species (2), whereas the synthesis in dichloromethane gives a five-coordinate zinc metalloporphyrin dimer (3) in the solid state. The pyrazine derivative crystallizes as a bis-pyrazine six-coordinate zinc metalloporphyrin (4). Complex 5 in the solid state is a dimer with 4,4′-bpy as a bridging ligand, whereas the 4,4′-mda species (6) is a five-coordinated monomeric zinc derivative in the solid state. All of structures of 2–6 possess cavities with different dimensions in which solvent molecules are located. The solution UV/Vis spectra of 2–7 exhibit redshifted Soret bands that indicate that these derivatives are five-coordinate zinc(II) porphyrin complexes in solution. UV/Vis titrations show that the association constants of 2–7 are close to those of known five-coordinate zinc(II) meso-porphyrins. The¹H NMR spectra of these species confirm this deduction. The photophysical proprieties of 1–7 are similar to those of related zinc(II) meso-porphyrins. The cyclic voltammograms of the H₂TPBP free base and 1–7 present a third one-electron reversible oxidation wave. Single-layer diode devices of the [iridium tin oxide/zinc porphyrin/aluminum] configuration show relatively low turn-on voltages.

Full text of DOI:10.1002/ejic.201600575

A Journal of
Accepted Article
Title: Synthesis, Electronic Spectroscopy, Photophysics and Electric Proper-
ties and X-ray Molecular Structures of the Aza Ligands tetrakis[4-
(benzoyloxy)phenyl]porphyrinato Complexes
Authors: Habib Nasri; Soumaya Nasri; Imen Zahou; Ilona Turowska-Tyrk; Thierry
´ ´
Roisnel; Eric Saint-Amant; Frederique Loiseau
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201600575
Link to VoR: http://dx.doi.org/10.1002/ejic.201600575

European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
Synthesis, Electronic Spectroscopy, Cyclic Voltammetry,
Photophysics and Electric Properties and X-ray Molecular
Structures of the dabco, pyz, 4,4’-bpy, 4-CNpy, 4,4’-mda Aza
Ligands Meso-tetrakis[4-(benzoyloxy)phenyl]porphyrinato
Complexes
Soumaya Nasri [a], Imen Zahou [b], Ilona Turowska-Tyrk [c], Thierry Roisnel [d], Fredérique Loiseau [e],
Eric Saint-Amant [e], Habib Nasri *[a]
Keywords: Zinc porphyrin complexes / Cyclic voltammetry / Aza ligands / Electronic spectroscopy / Fluorescence / Molecular structures
__________________________________________________________________________________
Abstract:
acting as a bridging ligand while in solid state, the 4,4’-mda
species (6) is a five-coordinated monomer zinc derivative. All
structures of 2-6 possess cavities with different dimensions where
are located the solvent molecules. The solution UV/Vis spectra of
2-7 exhibit redshifted Soret bands indicating that these
derivatives in solution are five-coordinated zinc(II) porphyrin
complexes. The UV/Vis titrations show that the values of the
association constants of 2-7 are close to those of known five-
coordinated zinc(II) meso-porphyrins. The proton NMR of these
species confirms this deduction. The photophysical proprieties of
1-7 are similar to those of zinc(II) meso-porphyrins related
species. The cyclic voltammetry of the H2TPBP free base and 1-7
present a third one-electron reversible oxidation wave. Single-
layer diode devices of the [iridium tin oxide / zinc porphyrins (1-7)
/ aluminum] configurations show relatively low turn-on voltages.
The synthesis of the new meso-porphyrin namely, tetrakis[4-
(benzoyloxy)phenyl]porphyrin (H2TPBP), the meso-(tetrakis[4-
(benzoyloxy)phenyl]porphyrinato)zinc(II)
starting
material
complex [Zn(TPBP)] (1) and the 1,4-diazabicyclo[2.2.2]octane
(dabco), pyrazine (pyz), 4,4’-bipyridine (4,4’-bpy), 4,4'-
diaminodiphenylmethane (4,4’-mda) and the 4-cyanopyridine (4-
CNpy) coordination compounds with the TPBP porphyrinate
complexes (2-7 respectively) are described. The preparation of
the dabco derivative in chlorobenzene leads a crystalline material
of a monomer five-coordinated zinc-porphyrin species (2) while
the synthesis in dichloromethane gives in solid state a five-
coordinated zinc metalloporphyrin dimer (3). The pyrazine
derivative crystallizes as bis-pyrazine six-coordinated zinc
metalloporphyrin (4). Complex 5 is present in solid state as a
dimer with the 4,4’-bpy
________________________________________________________________________________________________________________
light emitting diodes.[8] Understanding the effects of axial ligands
and the type of the peripheral groups of the porphyrin core of
Zinc porphyrins have been studied since the forties of the last
zinc
Introduction
century but for the last two decades a significant revivals of
metalloporphyrins on the electronic, redox, structural and
these investigations have been notice. This great interest
photophysical as well as other physical properties is very
concerning zinc porphyrins is explained by the use of these
important in order to use these species in the different
derivatives in many domains that extend from medicine, biology,
applications mentioned above. In this context, an important
chemistry and physics. Indeed, these applications include
number of investigations were carried out on the synthesis and
photodynamic therapy, photodynamic destructions of viruses,[1]
characterization of new porphyrins with different substituents on
chemical sensors,[2] semiconductors,[3] catalysis,[4] nonlinear
the porphyrin core with different donor, attractor as well as
optics,[5]
photovoltaic
materials.[6]
Metalloporphyrin-base
sterically hindered characters.[9,10,11,12]
molecular systems are also of interest in the field of molecular
electronic devices such as optoelectric memory devices
On the other hand, a number of zinc porphyrin complexes
involving monodentate N-donor neutral ligands such as
[7]
and
[13,14]
-
imidazole, pyridine
and anionic ligand such as N3 , NCS-
and CN- are reported in the literature.[15] Bidentate neutral N-
donor ligands (denoted aza ligands) such as 1,4-
diazabicyclo[2.2.2]octane (dabco), 4,4-bpyridine (4,4’-bpy), 4-
cyanopyridine (4-CNpy) and pyrazine (pyz) were also used in
many studies involving zinc metalloporphyrins.[16,17,18,19] It is
important to mention that several investigations were carried out
on zinc dimers and trimers where the porphyrins are related
together by different moieties known as spacers and the zinc
ions of these dimers or trimers (known as tweezers) are
[a]
Laboratoire de Physico-chimie des Matériaux, Faculté des Sciences
de Monastir, Avenue de l'environnement, 5019 Monastir, University
of Monastir, Tunisia.E-mail: habib.nasri2016@gmail.com
Laboratoire des Interfaces et des Matériaux Avancés, Faculté des
Sciences de Monastir, University of Monastir. Tunisia.
Faculty of Chemistry, Wrocław University of Technology, Wybrzeże
Wyspiańskiego 27, 50-370 Wrocław, Poland.
Centre de Diffractométrie X, Institut des Sciences Chimiques de
Rennes, UMR 6226, CNRS–Université de Rennes, 1, Campus de
Beaulieu, 35042 Rennes Cedex, France
[b]
[c]
[d]
coordinated to a bidentate ligand (dabco, pyz, …) (Scheme
24, 25]
1).[20,21,22,23,
Despite the important number of research
[e]
Département de Chimie Moléculaire, Université Grenoble-Alpes,
CNRS UMR 5250, BP53 38041 Grenoble, France
devoted to zinc porphyrin with bidentate aza ligands, a complete
characterization of these species are not found in the literature.
Herein, we describe, the synthesis of a new meso-porphyrin with
Supporting information for this article is available on the
WWW under http://dx.doi.xxxxxxxxxxxxxxxxxxxxxxxx
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European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
prepared in chlorobenzene while
3
was prepared in
an ester group (acting as -donor group) in para-positions of the
dichloromethane. The crystallization of these two species in
chlorobenzene (for 2) and dichloromethane (for 3) using n-
hexane as non-solvent leads to crystals of a monomer species
type 1/1-M (for 2) and a dimer derivative type 2:1-D (for 3) as
determined by X-ray molecular
phenyls
of
the
porphyrin:
the
meso-tetrakis[4-
(benzoyloxy)phenyl] porphyrin (H2TPBP), the starting material
[Zn(TPBP)] (1) and the zinc derivatives with the dabco, pyz, 4,4’-
bpy, 4-mda
respectively) (Scheme 2). These species are characterized by
UV/Vis, IR, H NMR spectroscopy and mass spectrometry (MS
and 4-CNpy aza ligands (complexes 2-7
1
structures.
MALDI-TOF and MS ESI). The association constants (Kas)
values of 2-7 are also reported. We shall also report the cyclic
voltammetry and the fluorescence results for all species that we
prepared. In addition, the electrical properties and the X-ray
molecular structures of the zinc metalloporphyrins with the
dabco, pyz, 4,4’-bpy and 4,4’-mda aza bidentate ligands are
reported. Notably, the 4,4’-mda derivative is the first report of a
zinc-porphyrin with this ligand and that a very few number of six-
coordinated structures of zinc metalloporphyrins with two N-
donor axial ligands are reported in the literature.
UV/Vis spectroscopy
As shown in Table 1, the free bases meso-porphyrins, including
the new H2TPBP porphyrin, present in solution similar UV/Vis
spectra with λmax values of the Soret band at ca. 420 nm and
four Q bands at ca. 515, 550, 590 and 650 nm. The [Zn(Porph)]
(Porph = meso-porphyrin) starting materials, exhibit similar
solution electronic spectra, which are slightly redshifted
compared to those of the free bases, with Soret bands at ca.
424 nm and Q(1,0) and Q(0,0) bands at ca. 550 and 590 nm
respectively. If we neglect the solvent effect, we notice that the
UV/Vis data of the free base meso-porphyrins and the
corresponding [Zn(Porph)] complexes didn’t depend on the
nature of the group of atom(s) in the para positions of the phenyl
rings of the meso-porphyrins (Table 1). Early investigations by
Valentine et coll.[13] on zinc(II) meso-tetraphenylporphyrin (TPP)
complexes with N-donor neutral monodentate ligand such as
pyridine and imidazoles (L) show that in solution, only the five-
coordinated [Zn(TPP)(L)] species are formed. Later on, several
studies have been reported in literature on monomeric zinc(II)
metalloporphyrins (type 1:1-M) (Scheme 2) and especially on
dimeric, trimeric (types 2:1-D and 3:2-T) and tweezer zinc
porphyrin derivatives (type 1:1-Tw).[20,22,26] These investigations
show that upon addition of N-donor bidentate ligands such as
dabco, pyz, 4,4’-bpy, to the tetra-coordinated zinc-porphyrin
starting material [Zn(Porph)], a bathochromic shift of about 10
nm is an indication of the formation of a monomer/L (type 1:1-M)
species while a redshift of about 5 nm indicates the formation of
1:1 tweezer/L (type 1:1-Tw) sandwich complex but in both cases
the zinc is five-coordinated.
Scheme 1. Schematic representations of different zinc-porphyrin / N-donor
bidentate ligands (L) coordination types.
The narrowing of the HOMO–LUMO gap is mainly due to the
deformation of the porphyrin core leading to redshifted Soret and
Q bands for porphyrins and metalloporphyrins.[27] The redshift of
the Soret and Q bands of the zinc(II) metalloporphyrins is also
related to the electron-withdrawing groups at the meso and β-
pyrrolic positions of the porphyrin and to the nature of the metal
ion.[28,29,30,31] The normalized absorption spectra of the starting
material [Zn(TPBP)] (1) and complexes 2-7 recorded in
chloroform are shown in Figure 1. The spectra were obtained by
dissolving crystals of 1-7 in chloroform. The max Soret band
values of these derivatives are practically the same (430 - 432
nm) which are redshifted by about 6 nm compared of the
[Zn(TPBP)] starting material (1). Therefore, since the redshifts
values of 2-7 are between 5 and 10 nm and according to what
has been mentioned above, it is not clear to tell from the redshift
values of the Soret bands whether 2-7 are monomer/L (type 1:1-
M) or dimer/L (type 2:1-D) species. Nevertheless, these UV/vis
data indicate that 2-7 are five-coordinated zinc(II)
metalloporphyrins. In order to calculate the values of the
association constants Kas of 2-7, titrations by UV/vis
spectroscopy were carried out in chloroform with concentrations
Scheme 2. N-donor bidentate ligands (aza ligands) used in this work.
Results and Discussion
Synthesis of 2-7
Complexes 2-7 were prepared by addition of an excess of the N-
donor aza ligands (dabco, pyz, 4,4’-bpy, 4,4’-mda and 4-CNpy)
to a solution of the [Zn(TPBP)] (1) staring material. It is
noteworthy that the dabco-zinc(II) derivatives 2 and 3 were
made using the same synthetic procedures except that 2 is
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European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
of about 10-6 M for the Soret region and 10-5 M for the Q bands
region. The titrations spectra of the [Zn(TBPP)] complexes by
the dabco, pyz , 4,4’-byp, 4,4’-mda and 4-CNpy ligands are
reported as supplementary information (Figures SI-1-10) along
with the estimated Kas values of 2-7 (Tables IS-1-2). The
titration data were analyzed using the non-linear regression
analysis program GWBASIC to determine the estimated Kas
values for complexes 2-7. The 4,4’-bpy derivative (5) exhibits the
highest value of Kas (2.72.106), the smallest value of Kas is
shown by the 4,4’-mda species (6) (0.59.103) while the Kas
values of the pyz and 4-CNpy derivatives (4 and 7) are 1.67.103
and 2.57.103 respectively. These titrations indicate a simple
binding process with the formation of monomer/L (type 1:1-M.
These values are in the range of the related species
[Zn(TPP)(L)] (L = pyridine, imidazole) for which the Kas values
are 2.52.104 and 6.61.104.[ 32,33 ]. By the other hand, the UV/Vis
titrations of the [Zn(Porph-Ia)] and [Zn(Porph-Ib)] complexes
(Porph-Ia and Porph-Ib are the two 5-phenyl-10-(2-
hydroxynaphthyl)-15-[4-hydroxyphenyl]
porphyrinato
enantiomers) with a pair of amino acid esters (L- and D-Phe-
OMe) leads to an estimated values of Kas of ~ 2.0.104 [34] which
are comparable to those of our zinc(II) metalloporphyrins (2-7).
The optical band gap (Eg-op) corresponds to the energy
difference between the levels of the HOMO and LUMO orbitals
of the metalloporphyrin (supplementary information Figure SI-
11). The values of Eg-op were obtain from the chloroform
UV/Vis spectra of 1-7 using the tauc'plot method. These values
in chloroform solution are ~ 1.97 eV which are higher than that
of the H2TPBP free base (1.82 eV) (Table 1).
Table 1. UV/Vis data of several free base meso-porphyrins, complexes 1-7 and a selection of zinc meso-metalloporphyrins.
_______________________________________________________________________________________________________________________
Compound
_______________________________________________________________________________________________________________________
Free base meso-porphyrins Solvent Soret band Q bands
λmax (nm) (ε.10-3)
Eog (eV) Ref.
_______________________________________________________________________________________________________________________
H2TPPa
H2TTPb
H2TPBP
CH2Cl2
CH2Cl2
CHCl3
419
420
420 (513)
516
516
516 (17)
552
552
552 (7)
594
594
591 (5)
645
650
646 (4)
-
-
[35]
[36]
this work
1.82
_________________________________________________________________________________________________________________________________________________________________________________________
[Zn(Porph)] complexes
Soret band
Q(0,0) band Q(0,0) band
_______________________________________________________________________________________________________________________
[Zn(TPP)]
[Zn(TTP)]
[Zn(TMP)]
[Zn(TPBP)] (1)
Toluene
CH2Cl2
CH2Cl2
CHCl3
422 (578)
421 (524)
420
549 (23)
550 (21)
550
588(4)
591 (25)
586
-
-
-
[37]
[35]
[12]
this work
425 (546)
554 (24)
596 (9)
1.99
________________________________________________________________________________________________________________________
L-zinc metalloporphyrins
(L = dabco. pyz. 4,4’-bpy, 4-CNpy and 4,4’-mda)
Soret band
Q(1,0) band
Q(0,0) band
________________________________________________________________________________________________________________________
[Zn(TPP)(3-AP)]c
CH2Cl2
CH2Cl2
CH2Cl2
Toluene
CHCl3
428
428
428
429
431 (502)
432 (498)
563
564
562
-
564 (21)
563 (20)
603
604
602
601
603(12)
604(12)
-
-
-
-
[17]
[17]
[12]
[38]
this work
this work
[Zn(TPP)(4-AP)]d
[Zn(TPP)(py)]
[Zn(TPP)(pyCCPh)]e
[Zn(TPBP)(dabco)].C6H5Cl (2)
[{Zn(TPBP)}2(2-dabco)]
.4(CH2Cl2).2(C6H14) (3)
[Zn(TPBP)(pyz)2].CHCl3 (4)
[{Zn(TPBP)}2(2-4,4’-bpy)].2CHCl3 (5)
[Zn(TPBP)(4,4’-mda)] (6)
[Zn(TPBP)(4-CNpy)](4-CNpy) (7)
1.97
1.97
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
430 (445)
430 (483)
431 (544)
430 (571)
561(18)
563 (20)
563 (27)
561 (23)
601 (9)
1.99
1.97
1.94
1.98
this work
this work
this work
this work
603 (12)
604(18)
601 (11)
________________________________________________________________________________________________________________________
a : H2TPP = meso-tetraphenylporphyrin. b : meso-tetratolylporphyrin. c : 3-AP = 3-aminopyridine. d : 4-AP = 4-aminopyridine.
e : pyCCPh = 4-phenylethynyl-pyridine.
10-6 M, recorded in chloroform. The inset shows enlarged views.
IR and 1H NMR spectroscopy
The IR spectra of 2-7 confirm the presence of the axial ligands.
Indeed, the 1:1-M and 2:1-D dabco-zinc deivatives 2 and 3
respectively exhibit sharp and medium intensity bands at ca.
3030 cm-1 attributed to s(CH) of the methylene group of the
dabco ligand. This absorption band is shifted to higher frequency
compared to the free dabco molecule (2885 cm-1) indicating the
coordination of this ligand to [Zn(TPBP)]. The presence of the
pyrazine ligand of complex 4 is confirmed by the absorption
bands at 2990 cm-1, 1416 cm-1 and 1040 cm-1. The absorption
bands of the C–H stretching frequencies of the starting material
[Zn(TPBP)] (1) and those of the 4,4’-bpy derivative (5) are
superposed (3063 cm-1 and 3034 cm-1) while the absorption
Figure 1. Electronic absorption spectra of complexes 1-7 at concentration ~
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European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
band at 1650 cm-1 is attributed to (C=C) of the 4,4’-bpy ligand.
For the 4,4’-mda-zinc derivative (6), the absorption bands at
3337 cm-1, 3282 cm-1, 1621 cm-1 and 818 cm-1 are attributed to
the coordinated 4-4’-mda ligand while the band at 494 cm-1
corresponds to the stretching frequency [Zn__N(4,4’-mda)].[39]
For 7, the IR spectrum exhibits a weak absorption band at 2238
cm-1 attributed to the nitrile stretching frequency (CN). The
value of this band is almost identical to the one of the free 4-
cyanopyridine (2236 cm-1) which could be attributed both to the
4-CNpy ligand or the free 4-CNpy molecule in 7 because, this
band is usually not affected by the coordination of the 4-
cyanopyridine.[40]
resonate at 6.85 ppm for the 2,6-H protons and 6.28 for the 3,5-
H3 protons. These values are close to those of the related
magnesium(II) 4-CNpy with the tetranitrooctaethylporphyrin
complex.[43]
As indicated by the 1H NMR data, the axial ligand protons of 2-7
are upfield shifted which is due to the shielding effect of the
porphyrin ring current.[43]
Fluorescence Spectroscopy
The fluorescence spectra of the H2TPBP and complexes 1-7
were recorded at room temperature in dilute dichloromethane
solution (~10-6 M) which show two bands Q(0,0) and Q(0,1)
(Figure 2). In Table 2 are summarized the maxima of the
fluorescence of the Q(0,0) and Q(0,1) bands, the fluorescence
quantum yields (f) and the fluorescence lifetimes (τf) of the
species just mentioned above and those of several related
species. The major difference between the zinc complexes 1-7
compared to their corresponding free base H2TPBP is the
remarkable hypsochromic shift of ~ 50 nm for the strongest
emission band Q(0,0) (except complex 2 where the blue shift is
~ 40 nm) and between 70 and 55 nm for the Q(0,1) band. This
shift is mainly due to the metalation of the porphyrin and it
seems that the axial ligand have minor effect except for complex
2 where the shift differ from those of the other zinc porphyrin
derivatives. By the other hand, the max values of the Q(0,0) and
Q(0,1) bands of 1-7 are close to those of the related zinc
porphyrin derivatives (Table 2). The fluorescence quantum yiels
of H2TPBP and complexes 1-7 are in the range [0.021 - 0.055]
which are close to the related zinc metalloporphyrins.[44]
The proton NMR spectra of 1-7 are given as supplementary
1
materials (Figures SI-13-20). Several investigations involving H
NMR titrations of tweezer-dabco zinc porphyrins reviled that
when less than 0.3 equiv is added to the zinc-porphyrin starting
material, the methylene protons of the dabco adduct appears as
sharp signal at ~ -5.00 ppm but for further addition of this ligand,
this signal is broadened and finally disappears.[41] The NMR
spectra of the dabco-zinc porphyrin species 2-3 didn’t show any
signals attributed to the methylene protons of the dabco ligand.
This could be explained by a fast exchange equilibrium between
the coordinated and the non-coordinated dabco to the
[Zn(TBPP)] species.
For complex 4 where Zn(II) is coordinated to a pyrazine ligand, a
weak singlet signal appears at 6.93 ppm which is upfield shifted
compared to the free pyrazine molecule ( = 8.59 ppm). Notably,
The Stokes shifts for 1-7 and H2TPBP, which are very small, are
1
typical of
a
fluorescence emission with no significant
the H NMR titration of a tweezer-pyz zinc porphyrin shows that
conformation change between the fundamental and excited
states. The singlet excited state lifetime was measured by
single-photon counting technique and the fluorescence decays
of 1-7 species were fitted
the coordinated pyrazine ligand appears at 6.12 ppm
corresponding to a tweezer/pyz type 1:1-Tw derivative.[42] The
very close chemical shift values of 4 and the tweezer/pyz
derivative is an indication that in solution, complex 4 is a five-
to single exponentials.
coordinated zinc metalloporphyrin. The 4,4’-bpy
non-
coordinated ligand presents two signals at 8.75 ppm (for the
1.4,6,7-H protons) and 7.53 (for the 2,3,5,8-H protons) (Scheme
2) ppm respectively. The protons of this ligand in complex 5 are
shielded and resonate at 6.25 ppm and 6.53 ppm. For the
monomer (1:1-M type) [Zn(TClPP)(4,4’-bpy)] (TClPP = meso-
[42]
tetrakis[4-chlorophenyl]porphyrinato)
related species, the 
values of the 1,4,6,7-H and 2,3,5,8-H protons are 6.20 ppm and
5.60 ppm respectively. By the other hand, the 4,4’-bpy protons
of the dimer/4.4-bpy (2:1-D type) species [Zn(TClPP)2(4,4’-bpy)]
[42]
are much more shielded at 4.30 ppm and 5.66 ppm. Thus,
the NMR data indicate that complex 5 in solution is a five-
coordinated zinc porphyrin derivative. For complex 6, the
protons of the 4,4’-mda ligand are slightly upfield shifted
compare to the free 4,4’-mda molecule for which the NH2,
1,4,7,8-H and 2,3,6,9-H protons (Scheme 2) resonate at ~ 4.00,
6.34 ppm, 6.81 and 3.81 ppm respectively. For 6, the chemical
shift values of the 4,4’-mda ligand are 2.63 ppm, 6.00 ppm, 6.75
ppm and 3.63 ppm respectively. The proton NMR of our 4-
CNpy-zinc(II) derivative (7) presents two doublets at 7.96 ppm
(for the 2,6-H protons, Scheme 2) and 8.75 ppm (for the 3,5-H3
protons) attributed to the non-coordinated 4-CNpy molecule. The
presence of a non-coordinated 4-CNpy in the lattice is confirmed
by the X-ray molecular structure (see crystallographic section).
The coordinated 4-CNpy ligand of 7 are upfield shifted and
Figure 2. The fluorescence spectra of H2TPBP and complexes 1–7 in CH2Cl2
(concentration ~10–6 M). The excitation wavelength is 540 nm.
The representative fluorescence decays for the free base
H2TPBP and complex 1 are shown in Figure 3 while the curves
of 2-7 are not shown as they resembles to complex 1. The f
values of the free base H2TPBP (~ 8 ns) is as expected much
higher than those of zinc metalloporphyrins 1-7 which are at ca.
1.6 ns except complex 2 which has the smaller f value of 1.3 ns.
Therefore, the life time value of zinc metalloporphyrins didn’t
depend on the axial ligand as shown also for the related species
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European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
[45]
[Zn(TPP)(IQNO)]
(IQNO = isoquinoline N-oxide) and
[Zn(TPP)(1,4-dioxane)2].[9]
Cyclic voltammetry
The electrochemical behavior of the H2TPBP porphyrin and 1–7
was studied by cyclic voltammetry (CV) with tetra-n-
butylammonium perchlorate (TBAP) as the supporting
electrolyte (0.1 M) in the non-coordinating solvent CH2Cl2 under
an argon atmosphere. The CV curves of H2TPBP and 1-7 are
depicted in Figure 4. The electrochemical data for H2TPBP,
complexes 1–7 along with those of several related species are
collected in Table 3. The free base H2TPBP exhibits two one-
electron reduction reversible waves and three one-electron
oxidation reversible waves which correspond to the reduction
and the oxidation of the porphyrin ring. The E1/2 values of
H2TPBP are close to close of meso-tetraphenylporphyrins
[49,45]
Figure 3. (a) : Fluorescence decay profile of the free base
H2TPBP (dark grey) and [Zn(TPBP)] (1) (light grey).
(H2TPP)] (Table 3).
Metallation of these porphyrins in
[Zn(Porph)] leads to a shift to more negative values of the
reduction and oxidation characteristic potentials.[12,51]
Table 2. Emission data of several meso-porphyrins and a selection of zinc
meso-metalloporphuyrins, max in nm and f in ns.
______________________________________________________________
Thereby, for H2TPBP, the values of the half potential waves are
0.95, 1.36, and 1.48 V for the first, second and third oxidations
waves respectively while those of complex 1 are 0.81, 1.11 and
1.40 V. The values of the E1/2 of the first, the second and the
third reduction waves of 1 are -1.48 V and -1.67 V respectively
compared to -1.12 V and -1.53 V for H2TPBP.
The coordination of the N-donor ligands (dabco, pyz, 4,4’-bpy,
4,4’-mda and 4-CNpy) leading to complexes 2-7 have a minor
effect on the oxidation and the reduction potentials compared
with the starting material [Zn(TPBP)] (Table 3).
Compound
Q(0,0) Q(0,1) f
f
Solvent Ref.
______________________________________________________________
Meso-porphyrins
H2TPP
H2TPP
H2TPP
H2TPBP
654
656
653
653
712
717
722
715
0.11
0.09
0.12
0.038
-
-
CH2Cl
CH2Cl2 [48]
[49]
8.2 CH2Cl2 this work
[46,47]
9.6 DMFa
Meso-porphyrin zinc(II) complexes
[Zn(TPP)]
[Zn(TTP)]
597
600
611
647
648
652
0.033 1.9 CH2Cl2 [36]
0.03
0.021
-
1.6 CH2Cl2 [15]
[Zn(TTP)(mbpy~py)]b
[Zn(TPP)(IQNO)]c
[Zn(TPP)(N3)]-
-
CH2Cl2 [50]
~602 656
1.9
et-acet d [51]
594
594
604
606
643
643
655
654
0.036 1.7 CH2Cl2 [15]
0.055 1.7 CH2Cl2 [15]
This is also the case for other zinc-porphyrin derivatives type
[Zn(Porph)(X)]±m (Porph = TPP, TMP and X = neutral or anionic
monodentate ligand, m = 0 or -1) (Table 3). The zinc-porphyrin
HOMO-LUMO gap can be expressed as the potential difference
of the first oxidation and the first reduction (supplementary
information Figure SI-12).[52] This energy gap is known as the
electrochemical gap (Eg-el). The calculated values of the energy
gap for 1-7 are in the range [2.15- 2.37] eV. These values are
close to the usual value of 2.25  0.15 eV for metalloporphyrins
[Zn(TPP)(CN)]-
[Zn(TPP)(1.4-dioxane)2]
[Zn(TPBP)] (1)
[Zn(TPBP)(dabco)].
C6H5Cl (2)
[{Zn( TPBP)}2(μ2-dabco)]
.4(CH2Cl2).2(C6H14) (3)
[Zn(TPBP)(pyz)2].
CHCl3 (4)
[{Zn(TPBP)}2(2-4.4-bpy)].
3CHCl3 (5)
-
1.8 dioxane [15]
0.027 1.6 CH2Cl2 this work
0.039 1.3 CH2Cl2 this work
0.046 1.6 CH2Cl2 this work
0.049 1.6 CH2Cl2 this work
612
606
596
596
660
654
644
645
654
0.044 1.5 CH2Cl2 this work
0.039 1.7 CH2Cl2 this work
[Zn(TPBP)(4,4’-mda)] (6) 606
[53]
and to the theoretical value of 2.18 eV given by Gouterman
[Zn(TPBP)(4-CNpy)]
and coll.[54] We notice that for 1-7, the values of the
.4-CNpy (7)
596
645
0.041 1.5 CH2Cl2 this work
______________________________________________________________
electrochemical gap (Eg-el) are quite higher compared to those
a DMF = N.N-dimethylformamide. b : mbpy~py = 4’-methyl-4-[2-(4-pyridyl)
c
d
of
the
optical
gap
(Eg-op).
ethenyl]-2.2’-bipyridine
: IQNO = isoquinoline N-oxide. et-acet = ethyl
acetate
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European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
Figure 4. Cyclic voltammograms of H2TPBP and 1 (the inset shows enlarged view): (a), complexes 2, 4 and 5: (b), complexes 3, 6 and 7: (c). The solvent is
CH2Cl2 and the concentration is ca. 10-3 m in 0.2 M TBAP, 50 mV/s, vitreous carbon working electrode (Ø = 3 mm).
Table 3. Electrochemical data a (in dichloromethane solvent) for complexes 1-7 and a selection of meso-porphyrins and zinc(II) metalloporphyrins.
____________________________________________________________________________________________________________________________
Ring Oxidations
2nd oxidation
(O2, R2)
Ring Reductions
1st oxidation
(O1, R1)
3th oxidation
(O3, R3)
1st reduction
(R4, O4)
2nd reduction
(R5, O5)
Ref
_____________
_____________
_____________
________________
_______________
b
c
d
Epa Epc
E1/2
Epa Epc
E1/2
Epa
Epc
E1/2
Epa
Epc
E1/2
Epa
Epc
E1/2
____________________________________________________________________________________________________________________________
H2TPP
H2TPP
-
-
-
-
1.02
1.08
-
-
-
-
1.26
1.35
-
-
-
-
-
-
-
-
-
-
-1.20
-1.21
-
-
-
-
-1.55
-
[50]
[47]
H2TPBP
[Zn(TPP)]
[Zn(TPP)]
[Zn(TMP)]
[Zn(TTP)
(1)
1.09 0.81 0.95
1.31 1.40 1.36
1.54 1.41 1.48
-1.17 -1.07 -1.12
-1.44 -1.62 -1.53
this work
[36]
[12]
[12]
[12]
this work
[12]
[12]
[12]
[12]
-
-
-
-
-
-
-
-
0.82
0.89*
0.83*
0.74
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-1.20
-1.26*
-1.44*
-1.22
-
-
-
-
-
-
-
-
-
1.18*
1.16*
-
-1.70*
-
-
0.84 0.78 0.81
1.15 1.06 1.11
1.35 1.44 1.40
-1.44 -1.53 -1.48
-1.63 -1.70 -1.67
[Zn(TPP)(Him)]f
[Zn(TPP)(2-Meim)]g
[Zn(TMP)(Him)]
[Zn(TMP)(2-Meim)]
[Zn(TPP)(N3)]-
[Zn(TPP)(CN)]-
(2)
-
-
-
-
-
-
-
-
-
-
-
-
0.65*
0.66*
0.58*
0.58*
0.71
-
-
-
-
-
-
-
-
-
-
-
-
1.35*
1.32*
1.21*
1.18*
1.15
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-1.35*
-1.40*
-1.50*
-1.55*
-1.53
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-1.70*
-1.75*
-
-
-1.76
-1.77
-
-
-
-
1.40
1.38
-
[15]
[15]
0.65
1.06
-1.51
0.92 0.75 0.84
0.85 0.78 0.80
0.90 0.74 0.82
0.86 0.75 0.81
0.84 0.79 0.81
0.84 0.78 0.81
1.20 1.04 1.12
1.12 1.05 1.09
1.19 1.04 1.12
1.17 1.06 1.13
1.44
-1.36 ~ -1.30 ~ -1.33
this work
this work
this work
this work
this work
this work
(3)
(4)
(5)
(6)
1.38 1.30 1.34
1.43 ~ 1.33 ~ 1.38
1.44 ~ 1.34 ~ 1.39
~ -1.38
~ -1.34*
-1.30*
-
-
-
-
-
-
1.28*
-
1.28*
-
-
-1.31 -1.35 -1.38
-1.47 -1.50 -1.52
-1.62 -1.75 -1.69
-1.64 -1.84 -1.74
(7)
1.14 1.05 1.10
1.37 1.34 1.36
____________________________________________________________________________________________________________________________
a :The potentials are reported versus SCE. b : Epa = anodic peak potential. c : Epc = cathodic peak potential. d : E1/2 = half wave potential. e : H2TMP = meso-
tetramesitylporphyrin. f : Him = imidazole. g: 2-Meim = 2-methylimidazole. *: denotes an irreversible wave.
Current–voltage measurements
As seen by the energy gaps values of 1-7 which are around 1.87
eV for the optical gap and in the range [2.15 – 2.36] eV for the
electrochemical energy gap, these species are considered as
semi-conductor materials which is the case of porphyrins and
metalloporphyrins. In order to have an idea about the electrical
properties of complexes 1-7, the following study was carried out.
Single-layer devices with the [ITO/ZnP(i)/Al] (i = 1-7 for
complexes 1-7 respectively) configuration were made to
investigate the current–voltage (I-V) characteristics of the zinc-
porphyrin species 1-7. Figure 5 displays the I-V curve measured
at room temperature, which exhibit diode-like with relatively low
turn-on voltages of 0.33, 0.70, 0.48, 0.40, 0.46, 0.65 and 0.35 V.
From the slope of I-V curves, the room temperature resistance is
Figure 5. Current-voltage curves of [ITO/ZnP(i)/Al] (i =1-7 for complexes 1-7
respectively).
estimated to be about 6.10, 52.80, 14.20, 9.00, 11.31, 56.56 and
116.00 k for complexes 1-7 respectively.
These features make these compounds promising active
materials for zinc metalloporphyrins-based OLEDs. The higher
conductivity of the staring material [Zn(TPBP)] complex (1)
compare to 2-7 could be explain by the absence of an axial
ligand in 1. This allows a better - overlap between the -
conjugated zinc-porphyrin derivatives compared to the five-
coordinated species. Notably, the crystal structures of 2-6
present voids with different dimensions while the crystal packing
of complex 7 shows supramolecular channels parallel to the c
[54]
axis (see crystallographic section)
which are for probably
responsible of the electric properties of 1-7. More studies are
underway to understand the disparity in the turn-on voltage and
the conductivity propriety of our zinc-porphyrin derivatives 1-7.
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European Journal of Inorganic Chemistry
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FULL PAPER
X-ray Structures of 2–6
of the 3-methoxypyrazine-zinc six-coordinated porphyrin species
[Zn(TPP)(Me-pyz)2] (MeO-pyz = 3-methoxypyrazine) with a
Zn__N(Meo-pyz) distance of 2.467 Å (Table 4). Complex 5 is
present in solid state as a dimer zinc metalloporphyrin type 2:1-
D where the 4,4’-bpy ligand is the bridging ligand. The
Zn__N(4,4’-bpy) bond length [2.178 (6) Å] is in the range [2.054
(4) - 2.270 (7) Å] of related species (Table 4). The 4,4’-
diamiadiphenylmethane zinc complex (6) is the first example of
a zinc metalloporphyrin species presenting a 4,4’-mda axial
ligand. This complex exhibits Zn__N(4,4’-mda) bond length value
of 2.208 (5) Å which is quite longer than the related non-
porphyrinic polymer complex {[Zn(2-L)(2-4,4’-mda)]}n (L= 5-
carboxybenzene-1,3-dicarboxylato) (Table 4). The coordination
geometries of 2-6 are reported as supplementary material
(Figure SI-29). The Zn__Zn distances in the two 2:1-D dimers (3
and 5) are 6.9567 (11) Å for the dabco derivative and 11.323 (2)
Å for the 4,4’-bpy species.
Complexes 2, 5 and 6 crystallize in the triclinic crystal system
with the space group P-1 which is also the case of complex 7
[54]. Complex 2 crystallizes in the monoclinic crystal system
(P21/n space group) while complex
4 crystallizes in the
tetragonal crystal system (I41/a space group) where the zinc lies
on a four-fold rotoinversion axis. The asymmetric unit of 2 is
made by one [Zn(TPBP)(dabco)] complex and one
chlorobenzene solvent molecule while the asymmetric unit of 3
contains one half [{Zn(TPBP)}2(2-dabco)] of a dimer complex,
two dichloromethane and one n-hexane molecules. For
complexes 4-6, the asymmetric units is made by one-quarter of
the [Zn(TPBP)(pyz)2] complex and one-quarter of a chloroform
molecule for the former complex, one half [{Zn(TPBP)}2(2-4-4’-
bpy)] of a dimer complex and one chloroform molecule for
complex 5 and one [Zn(TPBP)(4-4’-mda)] molecule for the later
complex (6). As shown in Table 4, zinc metalloporphyrins with
monodentate axial ligands are present in solid state as five-
coordinated species type [Zn(Porph)(X)]+m (X = neutral or
anionic ligand and m = 0 or 1)] (monomer type 1:1-M) in most
cases and as six-coordinated derivative type [Zn(Porph)(L)2] (L =
neutral axial monodentate ligand) (monomer type 1:2-M) in few
[31]
cases i.e. [Zn(TPP)(py)2]
and [Zn(TPP)(NH2Ph)2]
complexes.[56]
A search of the Cambridge Structural Database (CSD, Version
[57]
5.37)
revealed (i) dabco-zinc metalloporphyrins are present
as monomer/L type 1:1-M and tweezer/L type 1:1-Tw but there
is no reported dabco-zinc metallporphyrins as dimer/L type 2:1-
D, (ii) reported structures of zinc metalloporphyrins with pyz
ligand are monomers type 1:1-M, dimers type 2:1-D or six-
coordinated monomers type 1:2-M, (iii) the reported 4,4’-bpy-
zinc porphyrin derivatives are dimer type 2:1-D, trimer type 3:2-
D or polymers (type P), (iv) there is no 4,4’-mda zinc
metalloporphyrin reported in the literature.
The ORTEP drawings of 2-6 are illustrated by Figures 6-7. The
X-ray molecular structure of 2 is a monomer type 1:1-M zinc-
dabco species with the formula [Zn(TPBP)(dabco)].C6H5Cl while
complex 3 is a dimer type 2:1-D zinc-dabco derivative with the
formula
[{Zn(TPBP)}2(2-dabco)].4(CH2Cl2).2(C6H14).
For
complex 2, the Zn(II) cation is chelated by four pyrrole N atoms
of the porphyrinate anion and coordinated by nitrogen atom of
the dabco axial ligand in a distorted square-pyramidal geometry.
The dabco ligand in complex 3 links two [Zn(TPBP)] moieties
leading to a 2:1-D dimer species. The Zn__N(dabco) bond
lengths are very close (2.185 (2) Å and 2.182 (4) Å for 2 and 3
respectively) which are practically the same to the
[Zn(OEP)(dabco)] (OEP
=
octaethylporphyrinate) with
a
Zn__N(dabco) distance of 2.182 (2) Å.[58] These values are quite
different from those of zinc non-porphyrinic species (Table 4).
Our pyrazine zinc porphyrin derivative (4) is six-coordinated with
a Zn__N(pyz) distance of 2.459 (5) Å even though, in solution,
this species is five-coordinated as discussed in the UV/Vis
section. This value is considerably longer than those of the
related pyz-zinc porphyrins (Zn__N(pyz ~ 2.000 Å) and those of
pyz-zinc non-porphyrinic complexes where the Zn__N(pyz)
distance values range between 2.014 (4) [59] and 2.118 (2) Å [60]
Nevertheless, the high Zn__N(pyz) distance of 4 is close to that
.
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European Journal of Inorganic Chemistry
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FULL PAPER
Formal diagrams of the porphyrinato cores of 2-6 showing the
displacements of each atom from the mean plane of the 24-
atom porphyrin macrocycle in units of 0.01 Å are illustrated in
Figure 8. The porphyrin macrocycle of the dabco-zinc
monomer derivative (2) presents a major saddle and ruffling
deformations and a moderate doming and waving distortions.
The saddle deformation is due to the displacement of the
pyrrole rings alternately above and below the mean porphyrin
macrocycle so that the pyrrole nitrogen atoms are out of the
mean plane. The ruffling distortion is indicated by the high
values of the displacement of the meso-carbon atoms above
and below the porphyrin mean plane. The doming
deformation is originated by the displacement of the metal
atom out of the mean plane and the nitrogen atoms are
displaced toward the axial ligand. For the waving distortions,
the four fragments “(β-carbon)-(α-carbon)-(meso-carbon)-(α-
carbon)-(β-carbon)” are alternatively above and below the 24-
atoms of the C20N4 least squares plane (PC plane)[87]. The
porphyrin core of the dabco-zinc dimer species (3) is less
disordered than that of complex 2 with presents a moderate
saddle, ruffling. doming and waving deformations. The
pyrazine Zn(II) derivative (4), exhibits important ruffling,
waving and saddle deformations of the porphyrin ring. The
porphyrin cores of 5 and 6 are slightly disordered. It has been
noticed that for five-coordinated metalloporphyrins, the
average equatorial Metal-ion N(pyrrole) distance (M—Np) (M
= metal ion) and the distance between the metal atom and the
Figure 6. ORTEP diagrams of complex 2 : (a), complex 3 : (b) and complex
4 : (c). Ellipsoids are drawn at the 50% for 2 and 40% for 3 and 4.
mean plane made by the 24-atom core of the porphyrin
[88]
(M__PC) are related
(Table 4). This is also true for our
synthetic zinc porphyrins. Indeed, for the dabco derivatives (2
and 3), the Zn__Np and Zn__PC values are very close: 2.078
(2) Å / 0.415 (1) Å and 2.075 (4) / 0.415 (1) Å respectively.
The 4,4’-bpy and the 4,4’-mda derivatives (5 and 6) exhibit
close Zn__Np / Zn__PC values which are 2.063 (6) Å / 0.329
(2) Å and 2.064 (4) Å / 0.331 (1) Å respectively. The six-
coordinated bis(pyrazine) zinc(II) derivative (4) presents the
shortest Zn__Np distance value (2.027 (3) Å) and the Zn(II) ion
is in the plane of porphyrin core as is the case for six-
coordinated metalloporphyrins. By the other hand, for five-
coordinated metalloporphyrins,
a
higher value of the
Metal__PC distance is an indication of a better tendency of
coordination of an axial ligand to the central metal. Indeed, for
the five-coordinated zinc-derivatives 2, 3, 5,
6 and 7
complexes, the Zn__PC increase in the order : dabco (2-3)
[0.415(1) Å] > 4,4’-mda (6) ~ 4,4’-bpy (5) [0.331(1) Å and
0.329(2) Å respectively] > 4-CNpy (7) [0.319(1) Å] species [55]
.
This indicates that the dabco ligand have the best
coordination tendency to Zn(II) compared to the other aza
ligands.
Figure 7. ORTEP diagrams of complex 5 : (a) and complex 6 : (b). Only
one orientation of the disordered fragments is shown. Ellipsoids are drawn
at the 40% for 5 and 30% for 6.
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European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
Figure 8. Formal diagrams of the porphyrinato cores of complexes 2-6. The displacements of each atom from the 24-atom core plane in units of 0.01 Å are
illustrated.
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European Journal of Inorganic Chemistry
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FULL PAPER
Table 4. Selected bond lengths [Å] and angles [°] for 2-6 and some dabco, pyz, 4,4’-bpy and
4,4’-mda complexes.
[{Zn(OEP)}2(2-4,4’-bpy)]
[{Zn(TPP)}2(2-4,4’-bpy)]
2:1-D
2:1-D
2.080 (3)
2.081 (2)
2.065 (1)
2.059
2.049 (8)
2.058
2.173 (4)
2.169 (6)
2.270 (7)
2.371
2.185 (8)
2.490
2.223 (3)
2.311
2.342
0.517
0.327
0.286
0.011
-
[74]
[75]
___________________________________________________________________________
Complex
___________________________________________________________________________
b
c
d
Type a
M__Np
M__NL
M__PC
Ref
{[Zn(TMP)(4,4’-bpy)]}n
[{Zn(TPP)}3{2-4,4’-bpy)}2]
P
3:2-T
[76]
[75]
dabco-porphyrin complexes
[CoII(OEP)(dabco)]e
1:1-M
2:1-D
2:1-D
1:1-M
1:1-Tw
1:1-M
1.996 (5)
2.056
2.059 (5)
2.091 (6)
2.085
2.292 (7)
2.353
2.343 (5)
2.182 (2)
2.227
0.284
0.093
0.069
0.572
0.338
[58]
[61]
[60]
[58]
[62]
[{CoII(TPP)}2(2-4,4’-bpy)]
{[{CoII(TPP)2(2-4,4’-bpy)]}n
2:1-D
P
1.985 (3)
1.993
0.138
0.066
[77]
[78]
[{Os(TTP)(CO)}2(2-dabco)]
[{Ru(TTP)(CO)}2(2-dabco)]
[Zn(OEP)(dabco)]
[{Zn(TPBP)}2(2-4,4-bpy)].
3CHCl3 (5)
[Zn2(2-P1)(2-dabco)]f
[Zn(TPBP)(dabco)].C6H5Cl (2)
[{Zn(TPBP)}2(2-dabco)]
.4(CH2Cl2).2(C6H14) (3)
2:1-D
2.063 (6)
2.178(6)
0.329 (2) this work
2.078 (2)
2.185(2)
0.4324(5) this work
4,4’-bpy non-porphyrinic zinc complexes
[Zn(4,4’-bpy)(H2O)4]
[{Zn(L9)2}2(2-4,4’-bpy)]g
[Zn(L10)2(4,4’-bpy)2]g
1:1-M
2:1-D
1:1-M
-
-
-
-
-
2.117
-
-
-
[79]
[80]
[81]
2:1-D
2.075 (4)
2.182(4)
0.4151(1) this work
2.085 (2)
2.054 (4)
2.104 (4)
2.127
dabco-Zn(II) non-porphyrinic complexes
[{Zn(L1)}2(2-dabco)]g
2 :1-D
-
2.0123 (3)
2.123 (3)
2.123 (3)
2.297 (5)
2.117 (3)
2.116 (3)
2.24 / 2.37*
-
[63]
{[{Zn(NO2)(H2O)2}2(4,4’-bpy)]}n
P
-
[82]
[Zn(L2)(dabco)]g
[{Zn(L3)4}2(2-dabco)]g
[ZnL4(dabco)]
1:1-M
2:1-D
1:1-M
-
-
-
-
-
-
[64]
[65]
[66]
4.4-dma non-porphyrinic zinc complexes
[Cd(OAc)2(4,4-dma)2(H2O)2]j
[MnIICl2(4,4-dma)2(H2O)2]
[{CuIICl(L11)}2(2-4,4-dma)2]g
1:1-M
1:1-M
2:1-D
-
-
-
-
-
2.388
2.293
2.023 (6)
2.087 (5)
2.035 (3)
2.085 (3)
2.208 (5)
-
-
-
-
-
[83]
[84]
[85]
{[{Zn(Et)2}(2-dabco)]}n
P
-
-
[67]
pyz-Zn(II) porphyrin complexes
{[Zn(2-L12)(2-4,4-dma)]}n
[Zn(TPBP)(4,4-dma)] (6)
P
[86]
[Zn(TPP)(pyz)]
[{Zn(TPP)}2(2-pyz)]
1:1-M
2:1-D
2.062
2.210
0.282
0.352
0.339
0.043
0.000
0.190
0.100
[56]
[68]
2.064 (2)
2.057 (2)
1.994 (3)
2.060
2.065 (6)
2.057 (5)
2.027 (3)
2.211 (2)
2.179 (2)
2.036 (2)
2.467
2.190 (6)
2.235 (6)
2.459(5)
1:1-M
2.064 (4)
0.331 (1) this work
___________________________________________________________________________
[FeIII(TPP)(pyz)2]
1:2-M
1:2-M
2:1-D
[69]
[56]
[70]
a : See Scheme 2. b : Average equatorial metal–nitrogen pyrrole distance. : Distance between the metal and
c
[Zn(TPP)(MeO-pyz)2]h
[Zn2(2-P2)(2-pyz)]I
the nitrogen of the N-donor ligand. d : Distance between the metal atom and the mean plane made by the 24-
atom core of the porphyrin (PC). : OEP = octaethylporphyrinato. : 2-P1= 2-12,18,112,118,82,88,812,818
-
e
f
octahexyl-13,17,113,
117,83.87,813,817-octamethyl-2,7,9,14(1,3)
tetrabenzena-1,8(5,15)diporphyrina-
[Zn(TPBP)(pyz)2].CHCl3 (4)
1:2-M
0.012 (2) this work
4,5,11,12-tetrathiacyclotetradecaphane. g : Ln Ligands with L1 = (N,N-diethyl-dithiocarbamato-S,S'), L2 =
acenaphthylene-1,2-dione bis(4-ethylthiosemicarbazonato). L3 = O,O'-di-isopropyl dithiophosphato-S,S'). L4 =
bis(4-Allyl-3 thiosemicarbazonato) acenaphthenequinone. L5 = tri-t-butoxy silanethiolato-O,S. L6 = tri-t-butox
ysilanethiolato-S. L7 = O,O'-di-isopropyl dithiophosphato-S,S'. L8 = O,O'-di. Isopropyldithiophosphato-S. L9 =
1,3-di-phenyl-1,3-propanedionato). L10 = hydrogenphthalate. L11
carboxybenzene-1,3-dicarboxylato. MeO-pyz methoxypyrazin.
pyz-non-porphyrinic zinc complexes
[{Zn(L5)(L6)}2(2-pyz)]g
[{Zn(L7)(L8)}2(2-pyz)]g
[Zn7(OAc)(O)(pyz)2]j
2:1-D
2:1-D
1:1-M
P
-
-
-
-
2.118 (2)
2.072 (3)
2.072 (4)
2.014
-
-
-
-
[60]
[71]
[72]
[59]
=
chloro-malonic acid and L12 = 5-
k
h
:
i
:
2-P2 2-5,5'-(3,4,diethylpyrrol-
=
{[{Zn(sac)2(H2O)}2(2-pyz)]}n
2,5dyldimethylene)bis(2,3,7,8,12, 13,17,18-octaethylporphyrinate. j : OAc = acetate ligand.l:TOHPP=meso-
tetrakis(4-hydroxyphenyl) porphyrinato. k : sac = saccharinato. * : minimum / maximum of the six Zn__N(dabco)
distances.
4,4’-bpy porphyrinic zinc complexes
[{Zn(TOHPP)}2(2-4,4’-bpy)]l
2:1-D
2.032
2.097
2.134
2.144
0.306
0.308
[73]
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European Journal of Inorganic Chemistry
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The conventional and non-conventional hydrogen bonds and the C__H… intermolecular interactions of complexes 2-6 are listed in
Table S-1 (supplementary materials). The crystal packing of 2 is stabilized by non-conventional C__H…O and C__H…N hydrogen
bonds and by C__H… intramolecular and intermolecular interactions involving pyrrole and phenyl rings of the porphyrins
(supplementary information Table SI-3). Figure 9 illustrates the crystal packing of 2 shown that the chlorobenzene solvents occupy
the voids between [Zn(TPBP)(dabco)] complexes. In Figure 10 is shown the contents of the unit cell for complex 3 where we can see
that the disordered dabco axial ligand occupies the center and the summits of the cell. Within the crystal structure of 3. The
[Zn(TPBP)(dabco)] complexes are linked together via weak non-classical C—H…O hydrogen bonds and by C—H… intermolecular
interactions involving phenyl rings of the porphyrins (supplementary information Table SI-3).
The molecular structure of 4 shows the presence of non-classic C__H…O, C__H…N and C__H…Cl hydrogen bonds as well as C__H…
intramolecular and intermolecular interactions (supplementary information Table SI-3). Notably, the chloroform solvents are weakly
linked to four adjacent metalloporphyrins via C23__H23…Cl2 leading to three-dimensional framework (Figure 11). For complex 5, the
zinc-4,4’-bpy dimers with formula [{Zn(TPBP)}2(2-4,4-bpy)] are linked together by weak C__H…O non-conventional hydrogen bonds
and C__H… intermolecular interactions (supplementary information Table SI-3). The chloroform molecules are located near the 4,4’-
bpy axial ligand inside the dimers (Figure 12).
A drawing showing the crystal packing of complex 6 along the [100] direction is illustrated by Figure 13. The [Zn(TPBP)(4,4’-mda)]
complexes are linked together via weak non-classical C—H…O hydrogen bonds and by C—H… intermolecular interactions involving
pyrrole and phenyl rings of the porphyrins (supplementary information Table SI-3). Noteworthy the presence of weak oxygen-oxygen
non-contact interaction between the oxygens O8 of two adjacent metalloporphyrins (O8…O8 distance is 2. 919 Å). It is noteworthy
that the crystal structures of 1-7 possess voids with different dimensions where are located the solvent molecules in the case of
complexes 2-4 and 7.
Figure 9.The crystal structure of 2 showing the chlorobenzene solvents
occupying the voids between the [Zn(TPBP)(dabco)] molecules.
Figure 11. Projection of the crystal lattice of 4 down the a axis. The
disordered chloroform molecules (drawing in yellow) are located between
the [Zn(TPBP)(pyz)] complexes.
Figure 10. Projection along the [010] direction showing the contents of the
unit cell for complex 3.
Figure 12. A packing diagram of 5 showing the arrangement of the
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European Journal of Inorganic Chemistry
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FULL PAPER
[{Zn(TPBP)}2(2-4,4-bpy)] dimers and the chloroform molecules.
show relatively turn-on voltages between 0.33 and 0.70 V.
These proprieties could be explained by the presence of
voids in the crystal lattices of 1-7.
Experimental
General
All solvents and reagents were purchased from commercial supplies
and used without further purifications. 1H and 13C NMR spectroscopic
characterization were performed with a Bruker DPX 300 spectrometer.
Chemical shifts are reported as  (parts per million), downfield from
internal TMS. MALDI-TOF mass spectrometer (PerSeptive
Biosystems, Framingham, MA, USA), equipped with a 337 nm pulsed
nitrogen laser (20 Hz) and an Acqiris 2 GHz digitizer board, was used
for all experiments. These spectra were obtained in the positive mode
with the following settings: accelerating voltage 20 kV, grid voltage
62% of accelerating voltage, extraction delay time 100 ns. The laser
intensity was set just above the ion-generation threshold to obtain
peaks with the highest possible signal-to-noise (S/N) ratio without
significant peak broadening. All data were processed by using the
Data Explorer software package (Applied Biosystems). Mass spectra
were also recorded with a MicrOTOF Q Bruker instrument (ESI,
positive and negative modes). The mass spectra of the H2TPBP and
complexes 1-7 are reported as supplementary materials (Figures SI-
Figure 13. View down [100] showing the O__H…O hydrogen bonds linking
adjacent [Zn(TPBP)(4,4’-mda)] complexes via the oxygen atoms of the
TPBP porphyrinates.
CONCLUSION
We have successfully synthesized and characterized the new
meso-porphyrin : tetrakis[4-(benzoyloxy)phenyl]porphyrin, the
[Zn(TPBP)] starting material (1) and six zinc(II) species with
this porphyrin where the central atom is coordinated to the
dabco, pyz, 4,4’-bpy, 4,4’-mda and 4-CNpy aza ligands
(complexes 2-7 respectively). The X-ray molecular structures
of 2-6 show that the zinc(II)-dabco derivatives (2-3) are
monomer type 1:1-M (for 2) and dimer type 2:1-D (for 3).
Complex 4 is present in solid state as six-coordinated zinc(II)-
bis(pyrazine) species type 1:2-M. The zinc(II)-4,4’-bpy and
the zinc(II)-4,4’-mda derivatives (5-6) in solid state are dimer
type 2:1-D and monomer type 1:1-M respectively. The
molecular structure of the [Zn(TPBP)(4,4’-mda)] is the first
published structure of a zinc metalloporphyrin derivative with
the 4,4’-mda ligand. The crystal structure of these
metalloporphyrins show the presence of voids of different
dimensions where are located the solvents in the case of
complexes 2-4 and 7. The crystal packing of 2-6 are
stabilized by weak C__H…O, C__H…N and C__H…Cl hydrogen
bonds and by N__H…  and C__H… intermolecular interactions
involving phenyl and pyrrole centroid rings. In solution, the
UV/Vis and 1H NMR spectroscopy show that 2-7 are five-
coordinated zinc(II) metalloporphyrins which is confirmed by
UV/Vis titrations were the 4,4’-bpy zinc metalloporphyrin
species presents the highest association constant (Kas) value
while the 4,4’-mda and the pyz derivatives exhibit the smallest
values of Kas. The photophysical properties of 1-7 are normal
for zinc(II) metalloporphyrins. The cyclic voltammetry
investigation on these species show similar voltammograms
and that the half-wave potential values are close to those of
21-28). Fourier-transformer IR spectra were recorded on
a
PerkinElmer Spectrum Two FT-IR spectrometer. UV/Vis spectra and
titrations were recorded with a WinASPECT PLUS (validation for
SPECORD PLUS version 4.2) scanning spectrophotometer. The
emission spectra were recorded with a Horiba Scientific Fluoromax-4
spectrofluorometer with samples in dichloromethane at room
temperature. The samples were placed in 1 cm path length quartz
cuvettes. The luminescence lifetime measurements were performed
after irradiation at λ = 400 nm obtained by the second harmonic of a
titanium:sapphire laser (picosecond Tsunami Spectra Physics 3950-
M1BB laser with a 39868-03 pulse picker doubler) at a 8 MHz
repetition rate. A Fluotime 200 spectrometer from AMS technologies
was used for the decay acquisition. It consists of
a GaAs
microchannel plate photomultiplier tube (Hamamatsu 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. The luminescence decays were analyzed with the
FLUOFIT software from Picoquant. The emission quantum yields
were determined at room temperature by the optically dilute method
with samples in CH2Cl2 solutions.[89] [Zn(TPP)] in air-equilibrated
CH2Cl2 solution was used as a quanum yield standard (φ = 0.033).[36]
The experimental uncertainties were as follows: absorption maxima, 2
nm; molar absorption, 20%; emission maxima, 5 nm; emission
lifetimes, 10%; emission quantum yields, 20%. Electrochemical
measurements were performed with an Voltalab PGZ 40. All
experiments were performed with a conventional three-electrode
system comprising a modified GCE working electrode (3 mm in
diameter), a platinum wire auxiliary electrode and a saturated calomel
electrode (SCE) as the reference electrode. For the electrical
experiments, single-layer devices were elaborated as sandwich
structure between an aluminum (Al) cathode and an indium tin oxide
(ITO) anode. The zinc metalloporphuyrins compounds solutions (3.10-
2 M in chloroform) were spin-coated onto ITO glass. A thin aluminum
layer was deposited by thermal evaporation at 3.10-6 Torr.
the related [Zn(Porph)(L)]±m species (Porph
=
meso-
Synthesis Synthesis of the 4-formylphenylbenzoate
porphyrinato, L = neutral or anionic ligand and m = 0 , -1).
Nevertheless, a third reversible one-electron oxidation wave
is shown for the H2TPBP free base and 1-7 which is not
always the case for other meso-porphyrines and zinc
metallporphyrins. The electrical propriety of 1-7 were tested
using single-layer diode type [TIO/Zn-porphyrin/Al] devices
Benzoic acid (6 g, 0.049 mol.), 4-hydroxybenzaldehyde (6 g, 0,049
mol) and dimethylaminopyridin (DMAP) (0.6 g, 0.0049 mol.) were
dissolved at 0 °C in 20 mL of dichloromethane. To this solution 10 g
(0.040 mol.) dissolved in 30 mL of dichloromethane was added
dropwise and stirred at 0 °C and then at room temperature for 12 h.
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European Journal of Inorganic Chemistry
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Upon completion, the reaction mixture was filtered and the
dichloromethane was removed by rotary evaporator. The solution was
poured into water than the solid was filtered, washed with water than
hexanes and dried under vacuum to afford 9.3 g yellow-pale powder
(yield 86%), mp = 83 - 85°C, C14H10O3 : C 74.33, H 4.46%; found : C
74.81, H 4.35%. Spectroscopic analysis: 1H NMR (300 MHz, DMSO-
d6) (ppm) 10.04 (s, 1H), 8.17 (d, 2H, J = 6.2 Hz), 8.04 (d, 2H, J = 9.1
Hz), 7.80 (m, 1H), 7.64 (m, 2H), 7.56 (d, 2H, J = 8.9 Hz). 13C NMR (75
MHz, DMSO-d6) δ(ppm): 192.1 (C=O of CHO), 164.1 (C=O of
ester),155.2, 134.3, 134.0, 131.1, 129.9, 129.0, 128.5, 122.9.
Synthesis of the meso-tetrakis[4-(benzoyloxy)phenyl]porphyrin
(H2TPBP)
[Zn(TPBP)Cl]-. FTR-IR cm-1: 2960 (CH porphyrin), 1736 (C=O ester),
1264-1064 (C-O ester), 997 (CCH porphyrin).
Synthesis and crystallization of [Zn(TPBP)(dabco)].C6H5Cl (2),
[{Zn(TPBP)}2(2-dabco)] (3), [Zn(TPBP)(pyz)2].CHCl3 (4),
[{Zn(TPBP)}2(2-4,4’-bipy)].2CHCl3 (5), [Zn(TPBP))(4,4’-diam)] (6)
and [Zn(TPBP)(4-CNpy)].(4-CNpy) (7)
Complex 1 (0.086 mmol) was mixed with 2.2 equiv of the bidentate
ligand (dabco, pyz, 4,4’-bpy, 4,4’-mda and 4-CNpy) (0.190 mmol) in 5
mL of the solvents (CH2Cl2, CHCl3 or chlorobenzene). The reaction
mixture was stirred at room temperature for 2 hours. Crystals of the
desired complex were obtained by slow diffusion of n-hexane through
the chloroform, dichloromethane or chlorobenzene solution.
In a 100 mL two-necked flask, 4-formylphenylbenzoate (4.5 g, 19.9
mmol) were dissolved in 50 mL of propionic acid. The solution was
heated under reflex at 140 °C. Freshly distilled pyrrole (1.4 mL, 19.9
mmol) was then added dropwise and the mixture stirred for another
40 min. The mixture was cooled over night at 4 °C and filtered under
vacuum. The crude product was purified using column
chromatography (chloroform / petroleum ether = 4/1 as an eluent). A
purple solid was obtained and tried under vacuum (1.18 g, yield 21%).
C72H46N4O8 : C 78.96 H 4.23, N 5.12 %; found : C 78.14, H 4.34, N
5.21 %. Spectroscopic analysis: 1H NMR (300 MHz, CDCl3) δ(ppm)
8.97 (s, 8H, Hβ-pyrrol), 8.41 (d, 8H, J = 7.6 Hz), 8.32 (d, 8H, J = 8.3
Hz), 7.74 (t, J = 7.4, 4H), 7.65 (m, 16H), -2.74 (s, 2H, Hpyrrol). UV/vis
(CHCl3), λmax (nm) (ε.10-3 L.mmol-1.cm-1) 420 (513), 516 (17), 552 (7),
591 (5), 646 (4). MS (ESI+, dichloromethane): m/z = 1095.16
[H2(TPBP)]+. FTR-IR cm-1: 3316 (NH porphyrin), 2960 (CH porphyrin),
1736 (C=O ester), 1263-1263 (C-O ester), 967 (CCH porphyrin).
Complex 2 : C84H61ClN6O8Zn : C 72.94, H 4.44, N 6.08 %; %; found :
C 73.10, H 4.32, N 6.19%. 1H NMR (300 MHz, CDCl3) (ppm) : 8.93
(s, 8H), 8.40 (d, J = 9.1 Hz, 8H), 8.17 (d, J = 5.9 Hz, 8H), 7.75 (t, J =
6.2 Hz, 4H), 7.65 (m, 16H), 7.37 (m, 5H). λmax (nm) (ε.10-3 L.mmol-
1.cm-1) 433 (502), 564 (21), 604 (12). MS (ESI+, dichloromethane):
m/z = 1270.40 [Zn(TPBP)(dabco)]+. FTR-IR cm-1: 2920 (CH porphyrin),
1735 (C=O ester), 1260-1060 (C-O ester), 992 (CCH porphyrin), 3030
(CH dabco).
Synthesis of the (meso-tetrakis[4-(benzoyloxy) phenyl]
porphyrinato)zinc(II) complex [Zn(TPBP)] (1)
In a 100 mL one-necked round-bottomed flask, a mixture of the
H2TPBP porphyrin (400 mg, 0.365 mmol) and Zn(OAc)2.2H2O (700
mg, 3.650 mmol) in a solution of CHCl3 (30 mL) and CH3OH (5 mL)
were stirred at room temperature overnight. The mixture was washed
with water then the organic layer was dried over anhydrous MgSO4
and concentrated. A light purple solid of the [Zn(TPBP)] complex was
obtained (350 mg, yield 87.5%). C72H44N4O8Zn : C 74.64, H 3.83, N
4.84 %; found : C 74.81, H 3.94, N 4.98 %. Spectroscopic analysis: 1H
NMR (300 MHz, CDCl3) (ppm) 9.05 (s, 8H, Hβ-pyrrol), 8.41 (d, J =
6.3 Hz, 8H), 8.32 (d, J = 8.8 Hz, 8H), 7.73 (t, J = 9.0 Hz, 8H), 7.65 (m,
16H). UV/vis (CHCl3), λmax (nm) (ε.10-3 L.mmol-1.cm-1) 425 (546), 554
Complex 3 : C166H136Cl18N10O16Zn2 : C 67.78, H 4.66, N 4.76 %;
found : C 78.02, H 4.88, N 4.51%. 1H NMR (300 MHz, CDCl3)
(ppm) : 8.92 (s, 8H), 8.40 (d, J = 8.2 Hz, 8H), 8.21 (d, J = 8.7 Hz, 8H),
7.72 (t, J = 8.9 Hz, 4H), 7.64 (m, 16H). λmax (nm) (ε.10-3 L.mmol-1.cm-1)
431(485), 563(20), 604(12). MS (ESI+, dichloromethane): 1270,3
(25), 596 (9). MS (ESI-, dichloromethane): m/z
= 1193.40
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European Journal of Inorganic Chemistry
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FULL PAPER
[Zn(TPBP)(dabco)]+. FTR-IR cm-1: 2921 (CH porphyrin), 1736 (C=O
ester), 1258-1055 (C-O ester), 993 (CCH porphyrin), 3031 (CH dabco).
Complex 6 : C85H57N6O8Zn : C 75.30, H 4.24, N 6.20%; found : C
1
75.61, H 4.31, N 6.39%. H NMR (300 MHz, CDCl3) (ppm) : 8.98 (s,
8H), 8.41 (d, J = 7.8 Hz, 8H), 8.27 (d, J = 8.2 Hz, 8H), 7.73 (t, J = 8.4
Hz, 4H), 7.70 (m, 16H), 6.75 (d, J = 8.2 Hz, 4H), 6.00 (d, J = 8.4 Hz,
4H), 3.64 (s, 2H), 2.63 (s, 2H). UV-vis (CHCl3), λmax (nm) (ε.10-3
L.mmol-1.cm-1)
431 (544), 563 (27), 604 (18). MS (ESI+,
dichloromethane): m/z = 1356.8 [Zn(TPBP)(4,4’-mda)]+. FTR-IR cm-1:
2920 (CH porphyrin), 1731 (C=O ester), 12562-1060 (C-O ester), 993
(CCH porphyrin), 3337, 3282, 1621 and 818 (4,4’- mda ligand) at 494
cm-1 ([Zn-N(4,4’-bpy)]).
Complex 4 : C81H53Cl3N8O8Zn : C 67.65, H 3.71, N 7.79 %; found : C
68.02, H 3.90, N 7.59 %. 1H NMR (300 MHz, CDCl3) (ppm) : 9.01 (s,
8H), 8.40 (d, J = 8.3 Hz, 8H), 8.26 (d, J = 8.2 Hz, 8H), 7.73 (t, J = 6.1
Hz, 4H), 7.65 (m, 16H), 6.93 (s, 4H). λmax (nm) (ε.10-3 L.mmol-1.cm-1)
430 (445), 561 (18), 601 (9). MS (MALDI-TOF(+), dichloromethane,
+
with matrix): m/z = 1158.55 [Zn(TPBP)]
and m/z = 1238.27
[Zn(TPBP)(pyz)]+. FTR-IR cm-1: 2927 (CH porphyrin), 1734 (C=O
ester), 12561-1058 (C-O ester), 994 (CCHporphyrin), 2990, 1416 1040
(pyz ligand).
Complex 7 : C84H52N8O8Zn : C 73.82, H 3.83, N 8.20 %; found : C
73.69, H 3.71, N 8.39%. 1H NMR (300 MHz, CDCl3) δH, (ppm) : 9.01(s,
8H), 8.75 (d, J = 9.1 Hz, 2H), 8.42 (d, J = 6.3 Hz, 8H), 8.28 (s, 8H),
7.96 (d, J = 8.9 Hz, 2H), 7.74 (t, J = 9.2 Hz, 4H), 7.65 (m, 16H), 6.85
(d, J = 6.3 Hz, 2H), 6,28 (s, 2H). λmax (nm) (ε.10-3 L.mmol-1.cm-1) 430
(571), 561 (23), 601 (11). MS (ESI+, dichloromethane): m/z = 1262.66
[Zn(TPBP)(4-CNpy)]+. FTR-IR cm-1: 2966 (CH porphyrin), 1736 (C=O
ester), 1061 (C-O ester), 996 (CCH porphyrin), 2238 (4-CNpy ligand).
Complex 5 : : C156H98Cl6N10O16Zn2 : C 69.09, H 3.64, N 5.16 %;
found : C 69.31, H 3.78, N 5.39%. 1H NMR (300 MHz, CDCl3)
(ppm) : 8.97 (s, 8H), 8.67 (m, 4H), 8.40 (m, 8H), 8.25 (d, J = 7.2 Hz,
8H), 7.94 (d, J = 8.3 Hz, 4H), 7.73 (m, 4H), 7.62 (m, 16H), 6.62 (d, J =
5.1 Hz, 5H), 6.25 (m, 4H). λmax (nm) (ε.10-3 L.mmol-1.cm-1) 430 (483),
563 (20), 603 (12). MS (MALDI-TOF, dichloromethane, with matrix):
m/z = 1158.55 [Zn(TPBP)]+ and m/z = 1237.55 [Zn(TPBP)(py)]+. FTR-
IR cm-1: 2925 (CH porphyrin), 1735 (C=O ester), 1257-1063 (C-O
ester), 995 (CCH porphyrin), 3063, 3034 and 1650 (4,4’-bpy ligand).
Crystallography
The data collections for 2 and 5 were performed with a D8 VENTURE,
Bruker, diffractometer, the data for 3 and 4 were measured with an
APEXII, Bruker-AXS diffractometer while data for complex 6 were
collected using an Eos KM4, Oxford Diffraction, diffractometer
equipped with a graphite-monochromated Mo-Kα radiation source (λ =
0.71073 Å). The intensity data for all compounds were collected by
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European Journal of Inorganic Chemistry
10.1002/ejic.201600575
FULL PAPER
[5] R. A. Norwood, J. R. Sounik, Appl. Phys. Lett. 1992, 60, 295.
[6] H. Imahori, S. Hayashi, H. Hayashi, A. Oguro, S. Eu, T. Umeyama, Y.
Matano, J. Phys. Chem. C, 2009, 42, 18406.
the narrow-frame method at low temperature for complexes 2-5 and at
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scaled and corrected for absorption effects by using SADABS
[90]
program version 2.10 (Bruker AXS 2001) for complexes 2-5
and
SCALE3 ABSPACK in CrysAlis PRO program for complex 6 [91]. All
structures were solved by direct methods using SIR-2004 program [48]
and refined by full-matrix least-squares techniques on F2 by using the
SHELXL-97 program [92]. For 3, the dabco ligand is disordered on two
positions (C96-C97-C98 and C99-C100-101) with equal occupancies
(50%/50%) and one dichloromethane solvent is disordered in three
positions (C74A-Cl3A-Cl4A, C74B-Cl3B-Cl4B and C74C-Cl3C-Cl4C)
with occupancy factors 0.382(3), 0.445(3) and 0.174(3) respectively.
The anisotropic displacement ellipsoids (ADP) of the disordered
dichloromethane and the n-hexane are very elongated, which
indicates that there is static disorder in the molecular structure of 3.
For fragments involving these atoms, the DFIX, DANG and SIMU
[93]
constraint commands in the SHELXL-97 software were used
.
Complex 5 exhibits two disorder problems : the first, concerns one
arm of the TPBP porphyrinate where the « O7A-C66A-O8A-C67A-
C68A-C69A-C70A-C71A-C72A » and « O7B-C66B-O8B-C67B-C68B-
C69B-C70B-C71B-C72B » fragments presents the occupancy factors
0.526(11) and 0.474(11) respectively. The second disordered of 5
concerns the chloroform molecule which presents four positions: «
C78A-Cl1-Cl2-Cl3 », « C78B-Cl4-Cl5-Cl6 », « C78C-Cl7-Cl8-Cl9 »
and « C78D-Cl10-Cl11-Cl12» with occupancy factors of 0.426(3) ,
0.285(3) , 0.151(3) and 0.137(3) respectively. For these disordered
fragments, the ADP of these atoms are very elongated, which
required the use of DFIX, DANG and SIMU constraint commands.
For complex 6, the TPBP porphyrinate presents three disordered
arms. One of them is completely disordered in two positions : « C21-
C22-C23- the ester group: « C53-O6-C54-C55-C56-C57-C58-C59 »
and « C53-O6-C54-C55-C56-C57-C58-C59 » with major position
occupancy of 0.613(15). The ester group of a third arm of the TPBP
moiety is also disordered in two positions: « C66-O8-C67-C68-C56-
C69-C70-C71 » and « C66A-O8A-C67A-C68A-C56A-C69A-C70A-
C71A» with refined occupancy coefficients converged to 0.732(8) for
the major position. The ADP factors of these disordered fragments are
very elongated which required the use of the DFIX, DANG, FLAT and
SIMU constraint commands. All these disorders encountered during
the refinements of the structure of 6 explain the huge number of
restraints used. The crystallographic data, the structural refinement
details and a selected bond lengths and angles for 2–6 are reported
as supplementary
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Acknowledgement
The authors gratefully acknowledge financial support from the
Ministry of Higher Education and Scientific Research of
Tunisia. The present work was also partially supported by the
Labex Arcane (ANR-11-LABX-0003-01).
______________
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Table of Contents
Key Topic*: zinc porphyrin
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(benzoyloxy)phenyl]porphyrin (H2TPBP), the [Zn(TPBP)] starting material and the
dabco, pyz, 4,4’-bpy, 4,4’-mda and 4-CNpy zinc(II) complexes with the H2TPBP
porphyrin are described. These species were characterized by spectroscopy, cyclic
voltammetry and X-ray molecular structures. The electric properties of these
derivatives were also described.
Soumaya Nasri , Imen Zahou , Ilona
Turowska-Tyrk , Thierry Roisnel ,
Fredérique Loiseau , Eric Saint-Amant,
Habib Nasri
Page No. – Page No.
Page : Synthesis, Electronic Spectroscopy,
Cyclic Voltammetry, Photophysics and Electric
Properties and X-ray Molecular Structures of the
dabco, pyz, 4,4’-bpy, 4-CNpy, 4,4’-mda Aza
Ligands Meso-tetrakis[4-(benzoyloxy)phenyl]
porphyrinato Complexes
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This article is protected by copyright. All rights reserved