Kinetic and fluorescent properties of tetraphenylporphine derivatives in acetonitrile

Article abstract of DOI:10.1134/S0036023617080101

The kinetics of formation of zinc complexes with 5,10,15,20-tetra(4-Cl-phenyl)porphine and 5,10,15,20-tetra(4-NH₂-phenyl)porphine in acetonitrile in the range of 298–318 K are studied. It is found that peripheral substituents in tetraphenylporp

Full text of DOI:10.1134/S0036023617080101

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2017, Vol. 62, No. 8, pp. 1120–1126. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © Yu.B. Ivanova, A.S. Parfenov, N.Zh. Mamardashvili, 2017, published in Zhurnal Neorganicheskoi Khimii, 2017, Vol. 62, No. 8, pp. 1119–1125.
PHYSICAL CHEMISTRY
OF SOLUTIONS
Kinetic and Fluorescent Properties
of Tetraphenylporphine Derivatives in Acetonitrile
Yu. B. Ivanovaa, *, A. S. Parfenovb, and N. Zh. Mamardashvilia
aKrestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, 153045 Russia
bIvanovo State Medical Academy, Ministry of Health of the Russian Federation, Ivanovo, 153000 Russia
*e-mail: jjiv@yandex.ru
Received May 10, 2016
Abstract⎯The kinetics of formation of zinc complexes with 5,10,15,20-tetra(4-Cl-phenyl)porphine and
5,10,15,20-tetra(4-NH2-phenyl)porphine in acetonitrile in the range of 298–318 K are studied. It is found
that peripheral substituents in tetraphenylporphine can slow down or accelerate the reaction of formation of
zinc complexes in acetonitrile as observed by changes in kinetic rate constants. The fluorescence quantum
yields of tetraphenylporphine derivatives and their zinc complexes also depend on the presence of electron-
donating or electron-drawing substituents in the ligand structure.
DOI: 10.1134/S0036023617080101
The relevance of research in coordination chemistry targeted variation of coordination and acid–base prop-
is largely associated with the need to create novel types erties of porphyrins. The studies in this area are rather
of ligand systems, where the question regarding targeted intense due to the demand for novel luminescent mate-
synthesis of structures with preset geometry and elec- rials exhibiting certain photophysical properties. In this
tronic properties remains pivotal. Being typical ampho- work, we investigated the kinetics of formation of zinc
teric compounds (NH-acids and N-bases), porphyrins complexes of 5,10,15,20-tetra(4-Cl-phenyl)porphine
form metal complexes that exhibit the key biological, and 5,10,15,20-tetra(4-NH2-phenyl)porphine in aceto-
photochemical, catalytic, and enzymatic properties [1–
10], which depend on the coordination (electron donat-
ing/drawing) properties of the porphyrin molecule and
the metal. There is a strong chemical interaction
between a metal cation and the ligand in a metal por-
phyrin molecule, which promotes further coordination
of axial ligands, while retaining structural stability in
proton-donating media [1, 3]. Tetraphenylporphine
can be easily modified in the peripheral portion of its
molecule by inserting electron-donating and electron-
drawing substituents that exhibit their own electronic
and steric effects. These transformations in the macro-
heterocycle can significantly alter the coordination,
basic, and fluorescent properties of the ligand. Tetrap-
henylporphine complexes are widely used as model
compounds for bio- and physicochemical studies
focused on porphyrins, as well as a sensitizer in genera-
tion of singlet oxygen and as a component of organic
light-emitting diodes [8–10]. The structure and proper-
ties of porphyrin ligands within metal complexes allow
one to modify the peripheral portion of the molecule
and to build over and change the nature of the complex-
ing agent, thus contributing to designing materials with
target properties [11, 12].
nitrile in the temperature range of 298–318 K and the
fluorescent properties of these compounds and their
zinc complexes. Radiation in the red region of the spec-
trum was also measured, and the corresponding fluo-
rescence quantum yields were determined.
EXPERIMENTAL
The electronic absorption spectra (EAS) of the
solutions of ligands under study and their metal com-
plexes were recorded on a Cary 100 (Varian) spectro-
photometer. The fluorimetric measurements in aceto-
nitrile solutions of 5,10,15,20-tetra(4-Cl-phenyl)por-
phine (H2T(4-Cl-Ph)P), 5,10,15,20-tetra(4-NH2-
phenyl)porphine (H2T(4-NH2-Ph)P), ZnT(4-Cl-Ph)P,
and ZnT(4-NH2-Ph)P were carried out on a Shi-
madzu RF-5301 spectrofluorimeter. Kinetic studies
and data processing were performed in the same man-
ner as described in [13, 14]. Acetonitrile (which is a
bipolar aprotic solvent) of high purity grade (water
content <0.03%) was used as a solvent; the initial com-
pounds existed in the molecular form in acetonitrile as
shown by the initial spectra of porphyrins. Porphyrins
H2T(4-Cl-Ph)P and H2T(4-NH2-Ph)P were synthe-
The electronic and steric effects of the varied sub- sized using the procedures described in [15–17]. Zinc
stituents in the porphyrin macrocycle are the tools for acetate of pure for analysis grade was purified by
1120

KINETIC AND FLUORESCENT PROPERTIES
1121
Table 1. Spectral characteristics of the molecular species of porphyrins H2T(4-Cl-Ph)P and H2T(4-NH2-Ph)P and their
zinc complexes obtained in system 1*
λ4(logε)
λ3(logε)
λ2(logε)
λ1(logε)
Porphyrin
Soret
H2T(4-Cl-Ph)P
ZnT(4-Cl-Ph)P
H2T(4-NH2-Ph)P
ZnT(4-NH2-Ph)P
414(4.68)
421(4.95)
426(4.80)
429(4.86)
512(3.76)
546(3.64)
554(3.79)
562 (3.73)
561(3.88)
588(3.58)
594(3.61)
605sh(3.42)
606(3.90)
643(3.51)
–
522 (3.60)
–
–
657 (3.47)
–
* H T(4-Cl-Ph)P is 5,10,15,20-tetra(4-Cl-phenyl)porphine; H T(4-NH -Ph)P is 5,10,15,20-tetra(4-NH -phenyl)porphine;
2
2
2
2
ZnT(4-Cl-Ph)P is the zinc complex of 5,10,15,20-tetra(4-Cl-phenyl)porphine; ZnT(4-NH -Ph)P is the zinc complex of 5,10,15,20-
2
–1
–1
tetra(4-NH -phenyl)porphine; ε ((mol/L) cm ) is the molar extinction coefficient; the error of determination in three parallel
2
experiments ranged from 1 to 3%.
recrystallization from aqueous acetic acid and dehy- where Qx and Qref are the quantum yields of the sample
drated at 380–390 K [18].
under study and the reference sample, respectively; Ax
and Aref are their absorbances at the excitation wave-
length; Ix and Iref are the integral intensities; nx is the
refractive index of acetonitrile (1.3442); and nref is the
refractive index of toluene (1.4969).
Fluorimetric measurements of acetonitrile solu-
tions of H2T(4-NH2-Ph)P, ZnT(4-NH2-Ph)P,
H2T(4-Cl-Ph)P, and ZnT(4-Cl-Ph)P were carried out
on a Shimadzu RF-5301 spectrofluorimeter using the
following procedure:
(1) Acetonitrile solutions of the (H2T(4-NH2-Ph)P,
ZnT(4-NH2-Ph)P, H2T(4-Cl-Ph)P, ZnT(4-Cl-Ph)P)
samples under study with the absorbance A < 0.1 at the
excitation wavelength were placed in a quartz cell with
RESULTS AND DISCUSSION
The complexing properties of H2T(4-Cl-Ph)P and
H2T(4-NH2-Ph)P with Zn(OAc)2 in the H2T(4-Cl-
optical path length of 1 cm to eliminate the fluores- Ph)P,H2T(4-NH2-Ph)P–Zn(OAc)2–CH3CN system,
cence quenching effect.
herein system 1, were studied spectrophotometrically in
thermostated polished quartz cells at 298–318 K (at
least three replica experiments at each temperature)
(Figs. 1–3, Table 1). Temperature fluctuations during
the experiment were no more than 0.1 K. All spectra
of the reacting systems contained clearly observed
isosbestic points (Figs. 1 and 2).
(2) In order to avoid the error of determining fluo-
rescence intensity of the solution under study, we used
correction of dark current (the output current of the
non-irradiated photoelectronic multiplier).
(3) The effect of the solution (acetonitrile) on the
fluorescence intensity of the sample under study was
taken into account by subtracting the fluorescence
intensity of the pure solvent measured for the identical
parameters of the spectrofluorimeter
(4) Allowance for Rayleigh scattering was made by tion of porphyrin complexes with double charged
varying wavelengths within a broad range ( 40 nm) metal cations in non-aqueous solutions can be
until stable coordinates of the fluorescence peak of the described by the equation
corresponding sample were achieved (the fluores-
cence peak positions should not be changed with exci-
tation wavelength [19]).
(5) The resulting fluorescence spectrum of the sam-
ple under study in acetonitrile was compared to the lit-
erature data of the reference compounds: H2TPhP and
its zinc complex, for which the literature data on quan-
tum yields in toluene (0.11 and 0.033 [20]) are known.
The corresponding integral fluorescence intensities
were calculated.
The reaction of formation of metal porphyrins
under study in system 1 is of the first kinetic order with
respect to the ligand and salt (Figs. 1–3). The forma-
H2P + [MX2(Solv)n – 2] → MP + 2HX + (n – 2)Solv,
where X is an acido ligand, Solv is a solvent molecule,
n is the coordination number of the metal cation, H2P
is the porphyrin ligand (in our case, H2T(4-Cl-Ph)P
or (H2T(4-NH2-Ph)P), and M is the metal cation (in
our case, Zn2+).
The kinetic parameters at 298–318 K were calcu-
lated using the same procedure [13, 14].
For the confidence level of 0.90, the error in the
rate constant kv was 0.03 units. The Ea and ΔS≠ val-
ues were calculated for each replica experiment; the
averaged value was taken as the final variant. The error
was determined as the deviation from the arithmetic
mean. The kinetic parameters of reactions for the
coordination of porphyrins H2T(4-Cl-Ph)P and
(6) The fluorescence quantum yield of the porphy-
rin and metal porphyrin solutions in acetonitrile under
study were calculated using the conventional proce-
dure [21] according to the formula:
I x Aref nx2
Qx = Qref
,
Iref Axnr2ef
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 62 No. 8 2017

1122
IVANOVA et al.
log (C0/C)
(a)
(b)
A
308 K
2.0
A
0.6
0.5
0.4
0.3
0.2
0.1
0
0.16
298 K
318 K
0.14
0.12
0.10
0.08
0.06
1.5
1.0
0.5
500
550
600
650
λ, nm
390 420 450 480 510 540 570
0
200 400 600 800 1000 1200
λ, nm
τ, s
0
Fig. 1. (a) Evolution of EAS upon the coordination of H T(4-Cl-Ph)P to zinc acetate in system 1 at 298 K and (b) log(
)
c
H2P CH2P
2
as a function of τ for the reaction of formation of zinc complexes with H T(4-Cl-Ph)P in system 1 at 298, 308, and 318 K. c
=
2
porph
–5
–3
2.83 × 10 , and
= 2.07 × 10 mol/L.
c
Zn(OAc)2
log (C0/C)
(a)
(b)
308 K
298 K
A
2.5
2.0
0.7
0.6
0.5
0.4
318 K
A
0.3
0.2
0.1
1.5
1.0
0.5
0.3
0.2
500
600
λ, nm
700
0.1
0
0
0
50
100
τ, s
150
200
400
500
600
700
λ, nm
Fig. 2. (a) Evolution of EAS upon the coordination of H T(4-NH -Ph)P with zinc acetate in system 1 at 298 K and
2
2
0
(b) log(
) as a function of τ for the reaction of formation of zinc complexes with H T(4-NH -Ph)P in system 1 at 298,
2 2
cH P CH P
2
2
–5
–3
308, and 318 K. cporph = 2.01 × 10 , and
= 2.07 × 10 mol/L.
c
Zn(OAc)2
H2T(4-NH2-Ph)P with zinc acetate in system 1 are cost of the process decreases fivefold. Four electron-
summarized in Table 2.
donating substituents (–NH2) contribute to the
increase in electron density on tertiary nitrogen atoms,
thus accelerating complexation reaction 1. Four elec-
tron-drawing substituents (–Cl–) contribute to the out-
flow of electron density from the tertiary nitrogen
A conclusion can be drawn by summarizing the
resulting data that the electron-donating (–NH2) and
electron-drawing (Cl–) substituents have significant
effects on the complexing ability of the ligand: the rate
constant of formation of ZnT(4-NH2-Ph)P is 16-fold atoms, thus slowing down complexation reaction 1. If
higher than that of ZnT(4-Cl-Ph)P, while the energy one assumes the data on complexation of ZnTPhP
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KINETIC AND FLUORESCENT PROPERTIES
1123
–log keff
(a)
(b)
–log keff
2.3
3.4
2.2
2.1
2.6
2.7
2.6
2.7
–log CZn(OAc)2, mol/L
–log CZn(OAc)2, mol/L
Fig. 3. (a) –logk as a function of –log
for the reaction of formation of ZnT(4-Cl-Ph)P in system 1 at 298 K (the slope
c
Zn(OAc)2
eff
ratio: 1.02; the correlation coefficient: 0.998) and (b) –logk as a function of –log
for the reaction of formation of
c
eff
Zn(OAc)2
ZnT(4-NH -Ph)P in system 1 at 298 K (the slope ratio: 1.01; the correlation coefficient: 0.999).
2
[22] (Table 2) to be the reference point, the rate con- onance (σR), and the inductive (σI) components of the
stant of process (1) will increase 2.9- and 11.3-fold,
respectively, after electron-donating substituents
(‒OH, –NH2) were inserted. Insertion of an electron-
Hammett constants [24] and versus the weighted
Hammett constant (the sum of the σR and σI compo-
nents with weights [24–27]). The best fit was provided
by the logkv plots versus σp (Fig. 4) and versus
weighted Hammett constant (Fig. 5), which proved
the effect of the total inductive and resonance effect of
electron-donating and electron-drawing substituents
at positions 5 of meso-aryl moieties in tetraphenylpor-
phyrin on the reactivities of the corresponding com-
plexes. It is also possible that it is the transition state of
molecules (changes in length of N–H bonds), rather
than the number of intermolecular collisions in a
chemical process (vacuum), that has a direct effect on
the kinetics of the process in acetonitrile solutions of
the reaction system.
drawing substituent (-Cl–) will reduce the rate con-
stant of reaction (1) 1.4-fold. The energy cost of the
formation of zinc complexes decreases in the series
ZnT(4-NH2-Ph)P < ZnT(4-OH-Ph)P < ZnTPhP <
ZnT(4-Cl-Ph)P; this series is consistent with the data
[23] on the potential influence of the total (inductive
plus resonance) effect on the reactivity of a ligand
molecule. The ∆S≠ values constitute a similar series
for the reactions of formation of zinc complexes.
In order to elucidate the reason and the nature of
interactions, we plotted logkv versus the para (σp), res-
Table 2. Kinetic parameters of reaction for the coordination of porphyrins of tetraphenylporphine and its derivatives to zinc
acetate in the system 1 and the fluorescence quantum yields of tetraphenylporphine derivatives and their zinc complexes in
acetonitrile
298, (L mol)/s
kv
∆S≠, J/(mol K)
Qx
Ea, kJ/mol
Porphyrin
H2TPhP [22]
ZnTPhP [22]
0.059
0.017
0.302 0.029
0.875 0.018
0.212 0.011
3.405 0.092
70
60
95
22
2
3
3
2
–46
–53
38
2
2
2
5
H2T(4-OH-Ph)P [22]
ZnT(4-OH-Ph)P [22]
0.048
0.0169
H2T(4-Cl-Ph)P
ZnT(4-Cl-Ph)P
0.038
0.033
H2T(4-NH2-Ph)P
ZnT(4-NH2-Ph)P
0.2
0.18
–154
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 62 No. 8 2017

1124
log kv
IVANOVA et al.
log kv
0.5
0
0
–0.5
–0.5
–0.24
–0.16
–0.08
0.6σR + 0.4σI
0
0.08
–0.8 –0.6 –0.4 –0.2
0
0.2 0.4
0.6
σp
Fig. 4. Rate constant logk as a function of the weighted
Fig. 5. Rate constants logk as a function of the para Ham-
v
v
Hammett constant [24, 25].
mett constant [24, 26].
(a)
649.4
(b)
I
I
1
621.6
670.2
604.4
1
2
2
1.0
1.0
0.8
0.3
0.4
0.2
0
0.8
0.3
0.4
0.2
0
580 600 620 640 660 680 700 720 740
580 600 620 640 660 680 700 720 740
λ, nm
λ, nm
Fig. 7. Fluorescence spectra for (1) H T(4-NH -Ph)P (1.5 ×
Fig. 6. Fluorescence spectra for (1) H T(4-Cl-Ph)P (1)
2
2
2
–6
-6
–6
10 mol/L) and (2) ZnT(4-NH -Ph)P (1.5 × 10 mol/L)
(1.5 × 10
mol/L) and (2) ZnT(4-Cl-Ph)P (1.5 ×
2
‒6
in acetonitrile at 298 K; λ = 555 nm.
10 mol/L) in acetonitrile at 298 K; λ = 555 nm.
ex
ex
By analyzing the resulting data, one can draw a
The fluorescence spectra recorded for H2T(4-
conclusion that the quantum yields for the ligands
H2T(4-NH2-Ph)P (0.038), H2T(4-Cl-Ph)P (0.2) and
the corresponding metal complexes ZnT(4-NH2-Ph)P
(0.033) and ZnT(4-Cl-Ph)P (0.18) are virtually equal;
that is, the formation of metal complexes does not sig-
nificantly affect the photochemical properties of these
compounds, while in unsubstituted tetraphenylpor-
phine and its hydroxylated derivative, complexation was
NH2-Ph)P, ZnT(4-NH2-Ph)P, H2T(4-Cl-Ph)P, and
ZnT(4-Cl-Ph)P in acetonitrile are shown in Figs. 6
and 7 (the spectra were normalized to the maximum
fluorescence intensity). The fluorescence quantum
yields are listed in Table 2.
The error of fluorimetric measurements was ~10%.
The measurements were carried out at 295 K.
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KINETIC AND FLUORESCENT PROPERTIES
1125
accompanied by fluorescence quenching (the quantum phine and by the Russian Foundation for Basic
yield decreased almost threefold) [22] (Table 2). In Research (project no. 14-03-00011) in the part of
molecular photophysics, spin–orbit perturbations of studying the complexing properties of tetraphenylpor-
electronic states alter the photophysical parameters phine derivatives.
caused by enhancement of intercombinational transi-
tions (the heavy-atom effect) when heavy atoms are
inserted into the molecular systems [28]. The enhance-
ment of intercombinational transitions caused by the
heavy-atom effect results in fluorescence quenching
(reduction of the quantum yield) and shift in fluores-
cence peaks [28], which agrees with the results of our
experiment (the fluorescence peaks shifted by ~50 nm
(Figs. 6 and 7). A significant decrease in quantum yield
(by more than threefold) is observed for ZnTPhP and
ZnT(4-OH-Ph)P [22]. Changes in the fluorescence
quantum yields are observed for H2T(4-NH2-Ph)P and
H2T(4-Cl-Ph)P ligands compared to the unsubsti-
tuted H2TPhP: the fluorescence intensity of chloro-
substituted tetraphenylporphine increases (the quan-
tum yield rises ~3.4-fold).
Equipment at the Shared Use Center “Upper Volga
Regional Center of Physical and Chemical Research”
was used in our spectrophotometric studies.
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