Spectral, Acid, and Coordination Properties of Dodecasubstituted Porphyrins

Article abstract of DOI:10.1134/S107036321903040X

The results of investigation of the interrelation between the geometric structure and coordination, acid, and spectral properties of a series of porphyrins with different systems of meso and β substituents are presented. The geometry of polysubstituted porphyrins was optimized at the DFT B3LYP/6-311G level of theory using Gaussian 09. It was shown that the dianionic forms of dodecasubstituted porphyrins hold promise for the development of highly efficient liquid sensors for metal cations.

Full text of DOI:10.1134/S107036321903040X

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 3, pp. 586–596. © Pleiades Publishing, Ltd., 2019.
Russian Text © S.G. Pukhovskaya, Yu.B. Ivanova, Dao The Nam, A.S. Semeikin, S.A. Syrbu, N.Zh. Mamardashvili, 2016, published in Rossiiskii
Khimicheskii Zhurnal, 2016, Vol. 60, Nos. 5–6, pp. 53–64.
Spectral, Acid, and Coordination Properties
of Dodecasubstituted Porphyrins
S. G. Pukhovskayaa*, Yu. B. Ivanovab, Dao The Nama, A. S. Semeikina,
S. A. Syrbua, and N. Zh. Mamardashvilib
a Ivanovo State University of Chemistry and Technology, pr. Sheremetevskii 7, Ivanovo, 15300 Russia
*e-mail: svetlana.puhovskaya@mail.ru
b Krestov Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153040 Russia
Received June 15, 2016; revised March 22, 2019; accepted March 22, 2019
Abstract—The results of investigation of the interrelation between the geometric structure and coordination,
acid, and spectral properties of a series of porphyrins with different systems of meso and β substituents are
presented. The geometry of polysubstituted porphyrins was optimized at the DFT B3LYP/6-311G level of
theory using Gaussian 09. It was shown that the dianionic forms of dodecasubstituted porphyrins hold promise
for the development of highly efficient liquid sensors for metal cations.
Keywords: porphyrins, acid properties, coordination properties, kinetics
DOI: 10.1134/S107036321903040X
Porphyrins play an exceptionally important role in
natural biochemical and biophysical processes; they
are involved in the key biological, photochemical, and
enzymatic functions in nature.
Differences, often dramatic, in the physicochemical
properties that the same porphyrin complex incur-
porated in different protein supramolecular systems
exhibits are impossible to explain exclusively in terms
of the apoprotein composition. A critical factor for all
biological functions should be close interaction
between bound porphyrin units and the corresponding
apoproteins.
Tetrapyrrole-containing proteins belong to one of
the principal and most abundant classes of natural
enzymes. Over many years researchers have been
attempted to give a chemical explanation of numerous
biological reactions catalyzed by porphyrin-containing
protein complexes. Even though more than 150 types
of natural tetrapyrroles have been identified, there are
a lot of basic processes, where the mechanisms of
action of the porphyrin cofactor still remain to be clarified.
Furthermore, it was recognized that natural
porphyrin molecules exhibit a significant degree of
conformational flexibility. Thus, it turned out that the
protein, being a skeleton, exerts conformational control
of the porphyrin macrocycle and that a change in the
conformation of the macrocycle is an effective means
for fine-tuning the properties of porphyrins in natural
conditions and allows the same cofactor to be used for
different chemical reactions [1–5].
For example, heme is an active cofactor of oxygen
transport and storage (hemoglobin, myoglobin) and
also serves as an important link for the incorporation
of molecular oxygen into organic substrates (cyto-
chrome P450). It is involved in terminal oxidation
(cytochrome C oxidase) and H2O2 metabolism (catalase
and peroxidase) and catalyzes various electron transfer
reactions in cytochromes. In addition, during photo-
synthesis, the porphyrin cofactor can function as a
reaction-center pigment (charge separation) or as an
antenna pigment (exciton transition) in light-harvesting
complexes (for example, chlorophyll a).
Over the past few decades there has been rather
rapid revival of the chemistry of synthetic porphyrins.
Major successes have been achieved in the synthesis of
new structural types of porphyrins and their expanded
homologs or those containing substituted heteroatoms
in the macrocycle. The methods of synthesis and
modification of tetrapyrrole macrocycles have been
continuously improved.
586

SPECTRAL, ACID, AND COORDINATION PROPERTIES OF DODECASUBSTITUTED PORPHYRINS
587
Scheme 1.
R
R
R1
R
R
R4
R
N
NH
N
R2
R
HN
R3
1−7
1: 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin H2Br8TPP, R = Br, R1 = R2 = R3 = R4 = Ph;
R
R
2: 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(trifluoromethyl)porphyrin H2Br8T(CF3)P, R = Br, R1 = R2 = R3 = R4 =
CF3;
3: 5,10,15,20-tetrakis(4'-tert-butylphenyl)-2,3,7,8,12,13,17,18- octamethylporphine Н2ОМeT(4-t-BuPh)P,
R = Me, R1 = R2 = R3 = R4 =
t-Bu ;
4: 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)-2,3,7,8,12,13,17,18-octamethylporphine Н2ОМeT(3,5-t-BuPh)P,
t-Bu
R = Me, R1 = R2 = R3 = R4 =
;
t-Bu
5: 2,3,7,8,12,13,17,18-octamethyl-5,10,15,20-tetraphenylporphyrin H2OMeTPP, R = Me, R1 = R2 = R3 = R4 = Ph;
6: 2,3,7,8,12,13,17,18-octamethylporphyrin H2OMeP, R = Me, R1 = R2 = R3 = R4 = H;
7: 5,10,15,20-tetrakis(trifluoromethyl)porphyrin H2T(CF3)P, R = H, R1 = R2 = R3 = R4 = CF3;
8: 5,10,15,20-tetraphenylporphyrin H2TPP, R = H, R1 = R2 = R3 = R4 = Ph.
In addition, a powerful impetus for the develop-
ment of porphyrin chemistry was provided by the
discovery that the porphyrin macrocycle can exhibit a
significant degree of flexibility and can adopt different
conformations, which strongly affects not only the
physicochemical properties of porphyrins, but also
their reactivity. This, in turn, made it possible to
develop conformationally controlled models of bio-
systems and use the distortion of the porphyrin macro-
cycle as one of the most effective tools to control the
physicochemical and coordination properties of
porphyrins and their complexes [6, 7].
The main approach to obtain a distorted porphyrin
macrocycle involves introducing substituents into the
neighboring meso and β positions and, therewith, the
degree of distortion can vary substantially depending
on the number and size of the substituents. Over the
past decade many research groups have contributed
into chemistry of sterically distorted porphyrins. Let us
mention the most essential achievements in this
research field. Thus, Smith and co-workers synthesized
a wide range of porphyrins with a distorted macrocycle
[8–16]. Concurrently, a similar synthetic work was
carried out by Prof. Semeikin at the ISUCT [17–22].
This determines the relevance of research into the
interrelationship between the structure of model
porphyrins and their physicochemical and coordination
properties, which not only significantly expands the
basic concepts of chemical reactions with their parti-
cipation, but is also of interest for creating the
physicochemical fundamentals of new technologies.
Among polysubstituted porphyrins distorted by
multiple peripheral substitution, most attention has
been paid to octasubstituted tetraphenylporphine
derivatives containing β-alkyl, β-cycloalkyl-, and β-
halo groups, as well as octamethyl- and octaethyl-
porphyrins with successively increasing number of
meso-phenyl substituents [23–30]. This focus is first of
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PUKHOVSKAYA et al.
Table 1. Spectral characteristics of the molecular and double-deprotonated forms of dodecasubstituted porphyrins and the
logarithms of acidity constants in the AN–DBU system
Porphyrin
H2Br8T(CF3)P
Br8T(CF3)P2–
λmax, nm (log ε)
log Ka1,2
435 (5.0), 639 (4.1)
483 (4.6)
–6.78
H2Br8TPP
Br8TPP2–
470 (5.25), 568 (3.95), 622 (4.10), 738(3.85)
497 (5.30), 774 (4.80)
–10.77
–9.69
H2T(CF3)P
T(CF3)P2–
400 (5.23), 509 (4.14), 544 (4.13), 591 (3.84), 647 (4.11)
431 (4.96), 598 (4.00), 717 (3.89)
454 (5.61), 620 (3.65)
H2OMeTPP
OMeTPP2–
–11.65
–12.34
–13.03
440 (4.74)
Н2ОМeT(4-t-BuPh)P
ОМeT(4-t-BuPh)P2–
Н2ОМeT(3,5-t-BuPh)P
ОМeT(3,5-t-BuPh)P2–
468 (5.96), 691 (5.16),
444 (5.61), 544 (4.73)
467 (5.87), 691 (5.04)
442 (5.65), 541 (4.52)
all explained by the accessibility of such compounds.
They are generally synthesized by an improved
Rothemund method, which involves condensations of
β-substituted pyrroles and aldehydes containing meso
substituents [17, 31].
shifted red compared to the respective bands of the
planar analog H2OMeP (Δλ ≈ 70 nm for the first
absorption band and Δλ ≈ 65−50 nm of the Soret band;
see Table 1).
Strong electron-acceptor substituents in the meso
positions produce a blue shift of bands in the EA
spectra. Thus, the EA spectrum of H2T(CF3)P in the
Soret band region is shifted blue by 13 nm compared
to the spectrum of H2ТPP. Obviously, the introduction
of eight bulky substituents (bromine atoms) into the
pyrrole rings of porphyrin H2T(CF3)P, like with
H2ТPP, results in a distortion of the planar structure. In
the EA spectrum this is manifested in a considerable
red shift of the absorption bands: ~50 nm for the
H2ТPP derivative and a little less for the Br-
substituted H2T(CF3)P derivative.
In the present publication we analyze the spectral,
acid−base, and coordination properties of dodeca-
substituted porphyrins 1–5 in comparison with the
respective characteristics of their tetra- and octa-
substituted analogs 6–8 (Scheme 1).
Spectral and acid properties of dodecasub-
stituted porphyrins. Analysis of published [32-36]
and own data showed bulky substituents in the meso-
and β-pyrrole positions of the porphyrin macrocycle
strongly affect the geometry of porphyrins, and this
results in characteristics changes in their physico-
chemical properties, including the electronic absorp-
tion (EA) spectra. The spectral characteristics of the
studied porphyrins (Table 1), X-ray diffraction (XRD)
data [37, 38], and computer simulation suggests that β-
bromosubstituted porphyrin H2Br8TPP, as well as
dodecasubstituted derivatives of β-octamethylporphyrin
H2OMeP, H2ОМeT(4-t-BuP)P and H2ОМeT(3,5-t-
BuP)P, have a saddle-shaped macrocycle distortion.
For H2Br8T(CF3)P, a ruffle-type distortion of the por-
phyrin macrocycle was deduced; tetrasubstituted
porphyrin H2T(CF3)P has a less distorted, slightly ruffled
macrocycle. The absorption bands of porphyrins
H2ОМeT(4-t-BuPh)P and H2ОМeT(3,5-t-BuPh)P are
The acid properties of dodecasubstituted porphyrins
1–5 were studied by spectrophotometry in comparison
with H2T(CF3)P and H2ТРР in an acetonitrile (AN),
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) system; the
ionization constant of the conjugate acid of DBU in
acetonitrile (рKа) is 13.2 at Т = 298 K [39–44].
The acid–base interaction of porphyrins with a
strong organic base can be described by the equations:
Ka1
H+ + HP–,
H+ + P2–.
(1)
(2)
H2P
HP–
Ka2
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SPECTRAL, ACID, AND COORDINATION PROPERTIES OF DODECASUBSTITUTED PORPHYRINS
(a) (b)
589
Fig. 1. Changes in the EA spectrum in the course of titration of compound 1 (cp = 2.11×10–6 M) with a solution of DBU
(сDBU = 0–4.13×10–6 M) in AN at 298 K and the titration curve (λ = 469 nm).
The acidity constants for reactions (1) and (2) were
calculated by Eq. (3):
The characteristic spectral changes are shown in
Figs. 1–4, and Table 1 presents the spectral
characteristics of the deprotonated forms and the
logarithms of acidity constants of dodecasubstituted
porphyrins. It should be noted that in the AN–DBU
system we could not obtain the anionic forms of
H2ТPP [EA spectral parameters of the molecular form:
413 (5.02), 512 (3.56), 546 (3.12), 592, 646(2.96)] and
H2OMeP [EA spectral parameters of the molecular
form in CHCl3: 400 (5.61), 500 (4.60), 535 (3.96), 568
(3.68), 620 (3.65)] even at the highest concentration of
DBU in AN, which suggests that the latter two
porphyrins are less acidic than dodecasubstituted
derivatives.
log Kа1,2 = log(Ind) + nlogсDBU
.
(3)
Here Kа is the summary acidity constant; сDBU
,
analytical concentration of DBU in the solution; Ind,
indicator ratio P2–/H2P; and n, number of dissociated
protons (n = 2).
In the course of spectrophotometric titration, in the
EA spectra of compounds 1–5 we observed formation
of two families of spectral curves, each with its
specific system of isosbestic points.
As the concentration of the titrant (сDBU) was
increased, the EA spectrum of the molecular form of
porphyrins 1–5 (H2P) smoothly transformed into the
EA spectrum of the final form (dianion P2–).
The introduction of eight β-bromo substituents in
porphyrin 7 not only distorts the porphyrin macrocycle
(a)
(b)
Fig. 2. Changes in the EA spectrum in the course of titration of compound 2 (сp =1.16×10–5 M) with a solution of DBU
(сDBU = 0–1.4×10–3 M) in AN at 298 K and the titration curve (λ = 435 nm).
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PUKHOVSKAYA et al.
(a)
(b)
–5.40
Fig. 3. Changes in the EA spectrum in the course of titration of compound 3 (сp =1.16×10–5 M = 2.30×10–5 M) with a solution of
DBU (сDBU = 0–3×10–5 M) in AN at 298 K and the titration curve (λ = 468 nm).
and, as a result, leads to certain isolation of the π-
electron systems of the pyrrole and pyrrolenine
fragments, but also decrease the electron density on the
central nitrogen atoms of the reaction center because of
the electron-acceptor effect of the β substituents. This
facilitates proton abstraction under the action of the
organic base (DBU), and, therewith, the summary acid
dissociation constant of compound 2 is more than 3
orders of magnitude higher compared to compound 7.
However, the replacement of the trifluorophenyl group
by phenyl, while only slightly enhancing the
deformation of the porphyrin fragment, four orders of
magnitude decreases the summary acid dissociation
constant of compound 1.
The
quantum-chemical
calculations
were
performed using Gaussian 09 program package [45] at
the at the DFT B3LYP level of theory. The basis set 6-
311G was taken from the EMSL library [46–49]. The
calculated atomic coordinates were used to plot the
deviations of atoms of the porphyrin macrocycle from
the mean plane drawn through 24 carbon atoms.
The structures of porphyrins 1–4 optimized by the
B3LYP/6-311G method are shown in Fig. 5. The
calculation results The calculated data point to a high
degree of deformations of the porphyrin macrocycles.
The largest deviation of atoms is ~1.3−1.4 Å. It should
be noted that the meso-phenyl substituents in the β-
(a)
(b)
1.0
Fig. 4. Changes in the EA spectrum in the course of titration of compound 4 (сp = 1.8×10–6 M) with a solution of DBU (сDBU = 0–
2.5×10–6 M) in AN at 298 K and the titration curve (λ = 467 nm).
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SPECTRAL, ACID, AND COORDINATION PROPERTIES OF DODECASUBSTITUTED PORPHYRINS
(a)
591
(b)
(c)
(d)
Fig. 5. Deviations of atoms from the macrocycle mean plane drawn through 24 carbon atoms of the porphyrin macrocycle and the
porphyrin structures as given by B3LYP/6-311G calculations: (a) 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin,
(b) 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(trifluoromethyl)porphyrin, (c) 5,10,15,20-tetrakis(4'-tert-butylphenyl)-
2,3,7,8,12,13,17,18-octamethylporphyrin, and (d) 5,10,15,20-tetrakis(3',5'-di-tert-butylphenyl)-2,3,7,8,12,13,17,18-
octamethylporphyrin.
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PUKHOVSKAYA et al.
tetrasubstituted porphyrins H2T(CF3)P and H2TPP, the
acid properties of the porphyrins increase in the
following order 2 > 7 > 1 > 5 ˃ 3 > 4 > 8.
Kinetics of formation of zinc complexes of dodeca-
substituted porphyrins. The complex formation of
porphyrins with zinc acetate was studied by
spectrophotometry in a straight acetonitrile and an
AN+DBU binary solvent. This method is relevant,
because porphyrins and their complexes have strongly
different EA spectra.
The coordination of the porphyrin ligand with zinc
acetate in the individual acetonitrile is described by
Eq. (4):
Fig. 6. Change in the EA spectrum in the course of
coordination of compound 4 with zinc acetate (с = 1.5×
10–3 M) in AN at 298 K.
Н2P + [Zn(OAc)2(Solv)n–2
]
→ ZnР+2НOAc +(n – 2)Solv.
(4)
substituted porphyrin cause a sad-type distortion,
while the trifluoromethyl groups cause a strong
ruffling distortion.
The characteristics spectral changes are presented
in Fig. 6 on an example of compound 4.
Taking into account the deprotonation processes in
the AN + H2P + DBU and material balance equation (5),
by simple calculations we obtained the distributions of
molecular and deprotonated species of the studied
compounds in the course of titration (Fig. 7.)
The calculated structural parameters of poly-
substituted porphyrins 3 and 4 (Fig. 5) showed that the
phenyl rings are inclined at an angle of ~60°−70° to
the macrocycle plane and can affect the reaction center
exclusively through the σ-bond system (–I effect).
Consequently, the introduction of four phenyl sub-
stituents into the porphyrin macrocycle slightly
decreases the negative charge on the central nitrogen
atoms, there by facilitating N−H bond cleavage. The
methyl groups in the β-pyrrole positions of the
porphyrin macrocycle exert the opposite (+I) effect.
However, these factors only slightly affect the acid
properties of porphyrins 3 and 4. Much a stronger
effect is associated with distortion of the porphyrin
macrocycle. The second tert-butyl group in the
benzene ring of the meso substituent of porphyrin 4
causes an even stronger distortion of the macrocycle,
and this is consistent with the fact that porphyrin 4 is
less acidic compared to porphyrin 3, even though these
changes are within one order of magnitude [43].
c0 = c(Н2P) + c(P2–).
(5)
Knowing the points (Fig. 7), in which all molecules
transformed into doubly deprotonated species, one can
explore the formation of zinc complexes in the
AN+H2P+DBU system by an ionic mechanism. The
reactions involved in this process can be described by
Eq. (6):
[DBU·2H]2+P2– + [Zn(OAc)2(Solv)n–2
→ ZnР + 2HOAc + (n – 2)Solv + DBU.
]
(6)
Here OАс is the acido ligand; Solv, solvent molecule;
and n, coordination number of the metal cation. The
resulting data are collected in Table 2.
The EA spectra of all the studied systems contain
well-defined isosbestic points (a characteristic example
is shown in Fig. 8).
Thus, we found that all the studied porphyrin
ligands are protonated at the 1,8-diazabicyclo[5.4.0]
undec-7-ene concentrations in acetonitrile ranging
from ~10–6 to 10–3 M. The results of the present work
allowed us to develop the methods of stabilizing the
porphyrin substrates and measuring their concentra-
tion, based on choosing the deprotonation conditions
in a concrete system and specific spectral charac-
teristics of the substrates. As follows from the acid
dissociation constants of the series of highly distorted
dodecasubstituted porphyrins and less distorted
It was found that the rate of formation of the zinc
complex of porphyrin 4 is slightly higher both for the
ionic and molecular forms, compared to porphyrin 3.
However, these differences are within one order of
magnitude. Almost equal activation energies and
entropies are observed for both compounds within a
single mechanism, which is likely to be explained by
the fact that the second tert-butyl group only slightly
affects the reaction rate, because the electronic effect
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SPECTRAL, ACID, AND COORDINATION PROPERTIES OF DODECASUBSTITUTED PORPHYRINS
(a) (b)
593
(c)
(d)
(e)
Fig. 7. Distributions of molecular and doubly deprotonated porphyrins species in the course of titration: (a) H2Br8(CF3)P,
(b) H2Br8TPP, (c) H2T(CF3)P, (d) H2TOMeBr8(4-t-BuPh)P, and (e) H2OMeBr8(3,5-t-BuPh)P; (1) P2– and (2) H2P.
of the substituent in the case in hand can only be
transmitted through the σ-bond system.
showed that the reaction rate increases about 3–4
orders of magnitude in going from the molecular to
dianionic ligand species for compounds 1, 2, and 7 and
about 3 times for compounds 3 and 4. Therewith, a
decrease in the energy parameters of reaction (6) is
observed. This is likely to be explained by the absence
The study of the complex formation of zinc
complexes of porphyrins in acetonitrile and in the
presence of the strong organic base DBU (Table 2)
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PUKHOVSKAYA et al.
a high degree of distortion of the porphyrin
macrocycles. This, along with the electronic effects of
the substituents, enhances their acid properties
compared to the less distorted tetrasubstituted analogs
H2T(CF3)P and H2TPP. Naturally, the fact that the
calculations were performed for an isolated molecule
in a vacuum should not be neglected. However, the
revealed interrelationship between the geometric and
electronic structures of sterically distorted porphyrins
with their reactivity allows one to predict the effect of
the macrocycle distortion in differently substituted
porphyrins on their physicochemical and coordination
properties. In its turn, this opens ways to producing
new materials with desired properties. The reported
results showed that the rate of complex formation with
zinc acetate increases by 3–4 orders of magnitude in
going from molecular to dianionic forms of
porphyrins. The decrease in the activation energy of
the reaction is likely to be explained by the absence of
energy consumption for the deformation of and N−H
bond cleavage in the reaction center, as well as by a
stronger molecular polarization and, as a result, higher
degree of solvation of the anionic forms of porphyrins
in the transition state. Thus, the determination of the
conditions for the existence of dianionic forms of
porphyrins provides grounds for the development of
new sensory systems for detection and quantification
of metal cations in liquid media due to a sharp increase
in the rate of formation of metalloporphyrins in the
presence of an organic base.
Fig. 8. Changes in the EA spectrum in the course of
coordination of the dianion of compound 4 with zinc acetate
[с(Zn(OAc)2) = 0.3×10–3 M] in the AN–DBU–Zn(OAc)2
system at 298 K.
of energy consumption for the deformation of and
N−H bond cleavage in the reaction center, as well as
by a stronger molecular polarization and, as a result,
higher degree of solvation of the anionic forms of
porphyrins in the transition state. The replacement of
electron-acceptor substituents (атомов брома в β-Br
and meso-CF3) by electron-donor substituents in the β
positions and in the phenyl rinds sharply increases the
rate of complex formation, which is explained by the
increased electron density on the nitrogen atoms of the
reaction center.
In conclusion it should be noted that the calculated
geometries of the dodecasubstituted porphyrin point to
Table 2. Kinetic parameters of the formation of zinc porphyrin complexes in AN and AN–DBU
c(ZnOAc)2×103, cDBU×10–3,
kv298103,
ΔS≠,
Porphyrin
Solvent
CH3CN
Ea, kJ/mol
M
M
L mol–1 s–1
J mol–1 K–1
H2Br8T(CF3)P
H2Br8TPP
4.5
4.5
1.4
1.5
1.5
4.5
4.5
0.3
1.6
1.6
1.6
–
50±5
69±1
123±2
56±1
17±2
64±3
62±3
27±1
58±1
–88±2
–140±5
67±3
CH3CN
–
H2OMeTPP
CH3CN
–
18000±20
4267±10
4850±10
28.0±0,2
Н2ОМeT(4-t-BuPh)P
Н2ОМeT(3,5-t-BuPh)P
Br8T(CF3)P2–
CH3CN
–
CH3CN
–
62±5
CH3CN–DBU
CH3CN–DBU
CH3CN–DBU
CH3CN–DBU
CH3CN–DBU
CH3CN–DBU
1.5
–190±2
Br8TPP2–
0.05
The reaction is instantaneous
T(CF3)P2–
1.0
400600±500
24±1
–143±2
OMeTPP2–
0.018
0.016
0.0017
The reaction is instantaneous
ОМeT(4-t-BuPh)P2–
ОМeT(3,5-t-BuPh)P2–
11317±20
1523 ±20
39±1
34±1
3±1
–8±2
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SPECTRAL, ACID, AND COORDINATION PROPERTIES OF DODECASUBSTITUTED PORPHYRINS
595
Smith, K.M., Z. Naturforsch. B: Chem. Sci., 1995,
vol. 50, pp. 969–981.
FUNDING
The work was financially supported by the Russian
Foundation for Basic Research (project no. 16-53-
00100 Bel_a), and the synthetic part of the work was
funded by the Russian Science Foundation (project no.
14-23-00204).
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CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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