Interaction between meso-Phenyl-Substituted Porphirinioids and Carboxylic Acids, and a Thermal Analysis of Their Cationic Salts

Article abstract of DOI:10.1134/S0036024420010185

Abstract: Thermogravimetry and quantum chemistry, including NBO analysis, are used to study the thermal stability and NH acidity of single and double protonated forms of tetrapyrrole macroheterocyclic ligands (porphyrins, their inverted and N-substituted analogs, and corroles). The temperature ranges of the destruction of porphyrinium acetates and trifluoroacetates, the enthalpies of evaporation of acid molecules from the crystalline phase, and the composition of cationic salts are calculated. The structures of protonated forms of macrocycles are optimized. The energies of porphyrin–acid interaction and the values of charge transfer ??during the formation of bonds are calculated.

Full text of DOI:10.1134/S0036024420010185

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2020, Vol. 94, No. 1, pp. 110–118. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Fizicheskoi Khimii, 2020, Vol. 94, No. 1, pp. 98–107.
STRUCTURE OF MATTER
AND QUANTUM CHEMISTRY
Interaction between meso-Phenyl-Substituted
Porphirinioids and Carboxylic Acids,
and a Thermal Analysis of Their Cationic Salts
A. E. Likhoninaa, M. A. Krest’yaninovb, F. K. Morshneva, E. L. Kritskiia,
T. V. Kudayarovaa, and D. B. Berezina,*
a Research Institute of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and Technology,
Ivanovo, 153000 Russia
b Krestov Institute of Solution Chemistry, Russian Academy of Sciences,
Ivanovo, 153045 Russia
*е-mail: berezin@isuct.ru
Received March 13, 2019; revised March 16, 2019; accepted June 18, 2019
Abstract—Thermogravimetry and quantum chemistry, including NBO analysis, are used to study the thermal
stability and NH acidity of single and double protonated forms of tetrapyrrole macroheterocyclic ligands
(porphyrins, their inverted and N-substituted analogs, and corroles). The temperature ranges of the destruc-
tion of porphyrinium acetates and trifluoroacetates, the enthalpies of evaporation of acid molecules from the
crystalline phase, and the composition of cationic salts are calculated. The structures of protonated forms of
macrocycles are optimized. The energies of porphyrin–acid interaction and the values of charge transfer
during the formation of bonds are calculated.
Keywords: thermogravimetry and quantum chemistry, thermal stability, porphyrins, acetate degradation
temperature ranges
DOI: 10.1134/S0036024420010185
INTRODUCTION
employed to a lesser extent. At the same time, most
works devoted to studying the acid–base interactions
(ABI) of Н2Р and their analogs consider the state of
protonated forms of these macroheterocycles
(MHC) in solutions. The properties of the solid-
phase cationic salts of porphyrinium under polyther-
mal conditions remain unstudied; only processes of
the thermal decomposition of acid–base associates
of NH-active Н2Р with electron-donating molecules
have been discussed [20].
Interest in the chemistry of porphyrinoids (НnР)—
structural analogs of porphyrins (Н2Р)—has grown
rapidly over the last two decades. These compounds
are most widely used as promising components of new
materials for photoelectronics, catalysis, medicine,
and so on [1–6]. At the same time, some of their fun-
damental properties, knowledge of which is necessary
for the successful use of НnР, are unknown or yet to be
analyzed.
Formally, porphyrinoids of different classes can
be obtained from common porphyrins (e.g., com-
pound I) by performing a number of operations with
their molecules, e.g., N-substitution (II), contrac-
tion of the cavity of the MHC (III), and isomeriza-
tion via the inversion of pyrrole cycles (IVa, IVb), or
by changing the order of alternation of meso-carbon
The cationic forms of porphyrins and their ana-
logs that participate in all pH-dependent physico-
chemical processes have been studied intensively for
several decades [7–10]. The most popular ways of
studying acid–base equilibria are spectrophotometry
and spectropotentiometry [7, 11–14], along with
photophysical means [10, 15]. Calorimetric [16, 17]
and quantum chemical [8, 9, 18, 19] means are bridges [2, 21].
110

INTERACTION BETWEEN meso-PHENYL-SUBSTITUTED PORPHIRINIOIDS
Ph Ph Ph
111
NH
N
N
N
NH
NH
N
N
N
Me
Ph
Ph
Ph
Ph
Ph
HN
HN
HN
Ph
(I)
Ph
(II)
Ph
(III)
Ph
Ph
N
HN
CH
NH
CH
N
HN
N
Ph
Ph
Ph
Ph
N
HN
Ph
(IVa)
Ph
(IVb)
The aim of this work was to study the thermal sta- solvents ΔvapH (kJ/mol) from crystals of cationic por-
bility of cationic salts of HnP and perform a quantum- phyrinium salts were calculated graphically from
experimental data using the equation [20, 27]
chemical analysis of the depth of ABI between macro-
cycles with different configurations (i.e., the number
and locations of acid–base centers (I–IV), and car-
boxylic acid molecules (AcOH, TFA)).
3
Δ
vapH
R
1/2
dw
dτ
10
T
(3)
ln
T
= −
+ C,
(
)
where T is temperature, K; l = dw/dτ is the rate of mass
loss, mg/min; and R = 8.31 J/(mol K) is the universal
gas constant.
EXPERIMENTAL
Our objects of study (I–IV) were synthesized, puri-
fied, and identified spectrally according to the proce-
dures described in [22–25]. Chemically pure trifluo-
roacetic acid (Acros) was distilled with a reflux con-
denser. Acetic acid of the same grade (Khimreaktiv)
was purified following the recommendations in [26].
The content of water in the solvents, estimated via
Fischer titration, was less than 0.1%.
Thermogravimetric studies were performed on a
STA 449 F3 JUPITER (NETZSCH) derivatograph
that allowed synchronous thermal analysis. A crystal-
line sample weighing about 5 mg was placed in a plat-
inum crucible and heated in a static argon atmosphere
at a rate of 5 K/min in the temperature range 298–
1223 K. Samples of solid cationic salts of the compo-
sition H(n+1)P+X– or H(n+2)P2+ (X–)2, formed accord-
ing to the equations
Thermogravimetric experiments were repeated
several times. The error in measuring the temperatures
of the stages of mass loss (t, °C), and in calculating the
enthalpies of evaporation (ΔvapH) was no more than
10%. The composition of the cationic salt was calcu-
lated from a thermal curve based on the weight of the
sample, the number of stages of thermal decomposi-
tion, and the weight loss at each of them. The experi-
mental and calculated data are given in Table 1.
The geometric parameters of macrocycles I–IV,
and the products of their interaction with one or two
acetic and trifluoroacetic acid molecules, were opti-
mized using the GAUSSIAN 09 software package
[28], the density functional theory, the B3LYP hybrid
functional [29], and the CC-pVDZ basic set [30]. In
our NBO analysis, the energies of interaction between
acid–base centers (Еint) were calculated along with the
energies of stabilization (Estab) of the proton orbitals
that form hydrogen bonds with electron pair donors,
the charge transferred to them (qstab), and the geome-
HnP + HX ꢀ Н(n+1)Р+Х–,
(1)
HnP + 2HX ꢀ Н(n+2)Р2+(Х–)2
(2)
were obtained by evaporating saturated solutions of try of the H-bonded reaction center forms of MHC
macrocyclic compounds in the corresponding proton- [31, 32]. A full description of the calculation proce-
donor solvents (AcOH, TFA) to a constant mass at dure was given in [18], and our data are presented in
303–313 K. The enthalpies of evaporation of bound Table 2.
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LIKHONINA et al.
Table 1. Composition and thermal degradation of cationic salts of macroheterocycles I–IV in an inert medium
Destruction of the cationic salt of porphyrinium
Destruction
of MHC
other decomposition
products
Molar ratio
evaporation of Н2О
evaporation of НХ
/nНХ/nMHZ
n
H2O
tonset1, tmax1, tfin1, ∆vapH(1), tonset2, tmax2, tfin2, ∆vapH(2), tonset3, tmax3, tfin3, ∆vapH(3)
,
tonset, tmp,
°C °C
°C °C °C kJ/mol °C
°C
°C kJ/mol °C
°C
°C kJ/mol
АсOH
II 79
III 69
IV 63
97 116
87 108
72 88
33
29
187
128 142 156
130 149 162
53
46
—
198 211 224
203
—
—
4/2/1/1*
6/1/1
4/1**
427 421
—
—
—
—
—
—
308
—
—
—
—
357 358
TFA
I
88 107 122
II 84 103 110
III 71 98 110
IV 72 103 114
135
35
38
47
184 206 220
168 189 198
133 156 176
185 204 216
60
35
48
99
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
15/2/1
13/2/1
6/1/1
7/1/1
470
426
309
354
—
—
—
—
t
, t , and t are the temperatures of the beginning, maximum effect, and end of the thermal decomposition stage.
onset max
fin
.
HX MeCOOMe MHC
*
/n /n
/n
nH O
2
**
+ n /n
.
n
H2O
HX MHC
RESULTS AND DISCUSSION
The configuration of the N-basic centers in the
depending on the nature of the MHC, starts to be
removed from porphyrinium acetate at tonset = 63–
79°C with enthalpy of evaporation ΔvapH(1) = 29–
33 kJ/mol, and from trifluoroacetate at tonset = 71–
88°С with ΔvapH(1) = 35–135 kJ/mol. An average of 2
to 6 water molecules are usually released during the
thermal decomposition of porphyrinium acetates, and
6 to 15 molecules during the thermal decomposition of
their trifluoroacetates. Based on one water molecule,
the average enthalpy of its evaporation for different
НnPs varies from 3 to 9 kJ/mol (Table 1).
porphyrin molecules (compound I) and their struc-
tural analogs (II–IV) considered in this work differed
considerably. In acidic media, meso-tetraphenylporfin
(I), like most H2Ps, forms symmetric N,N'-dication-
ions (1), (2) [7–9, 11, 15, 16]. An intracyclic methyl
group introduces asymmetry into the molecule of
N-substituted porphyrinoid (II), as a result of which
the N-basic centers become non-equivalent [7, 12,
33–35]. Corrole (III) forms a stable N-monocation,
while its subsequent protonation on a Cmeso carbon
atom with the destruction of the aromatic π-system of
the macrocycle is possible only in high acid environ-
ments (H2SO4, TFA) [21]. Inverted porphyrinoid (IV)
can exist in the form of two tautomers, in one of which
both N-centers are inticyclic (IVb); in the other, one
of them migrates to the periphery of molecule (IVa)
[12, 19, 33, 34].
Evaporation of acid molecules from cationic salts
of MHC I–IV begins in the temperature range of 128
to 185°С. Unlike trifluoroacetic, the removal of acetic
acid is independent of the nature of the macrocyclic
base (128–130°С; ΔvapH(2) = 46–53 kJ/mol, Table 1).
The enthalpy of acid evaporation from the porphy-
rinium salt is largely determined by the energy of inter-
action between tertiary nitrogen atoms of the MHC
and acid protons. Considering the number of evapo-
rated AcOH molecules, corrole III may therefore be
considered a more basic MHC than II (Table 1).
Despite our expectations, the heterogeneity and
asymmetry of the localization of the main centers in
the molecules of porphyrinoids II–IV do not manifest
in an increase in the number of peaks on the thermal
destruction curves of their cationic salts (1), (2). The
thermogram of the cationic salt of the porphyrinoid
In contrast to solutions, the crystal lattice can con-
tribute to ΔvapH(2) in the solid phase. The series of
НnP (II–IV), like the thermocurve of the porphyrin- changes in the enthalpy of evaporation of TFA (ΔvapH(2),
ium salt (I, Figs. 1, 2), normally includes three stages kJ/mol) per one molecule of acid, IV (99) > III (48) >
of destruction: two in the low-temperature region, I (30) > II (17.5) is not entirely consistent with the
corresponding to the cleavage of the molecules of change in the basicity of macrocycles. It is well
bound water and acid, and one in the high-tempera- known that porphyrin I has the weakest affinity for
ture region, associated with the thermal decomposi- protons, relative to considered porphyrinoids II–IV
tion of the macroheterocycle (Fig. 1, Table 1). Bound [21, 35, 36]. The evaporation of the bound acid
water, which is always present in the cationic salt, from the dicationic salt crystal of macrocycle II,
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INTERACTION BETWEEN meso-PHENYL-SUBSTITUTED PORPHIRINIOIDS
115
ТG, %
100
DCC, mW/mg
0.6
Change in mass: −25.68%
0.4
0.2
0
80
60
40
20
−0.2
[1]
[1]
−0.4
−0.6
−0.8
Change in mass: −19.51%
100 200 300 400 500 600 700 800 900
t, °C
2+
−
Fig. 1. (Color online) Thermogravimetric and DCC curves of the dicationic salt of compound I (H TPP (CF COO ) ) ·
4
3
2
nH O.
2
ТG, %
100
DTG, %/min
1
[1]
0
90
80
70
60
50
Change in mass: −10.97%
−1
−2
−3
Change in mass: −27.36%
−4
−5
[1]
100 200 300 400 500 600 700 800 900
t, °C
Fig. 2. (Color online) Thermogravimetric integral and differential curves of the nanostructured dicationic salt of compound IV
with the composition ( + n )/n = 4/1.
nH O
НХ
МНC
2
which has a strongly nonplanar structure [33], is only one acid molecule during the thermal decompo-
apparently greatly facilitated, compared to the flat-
ter compound I.
sition of its acetates and trifluoroacetates.
Another anomaly in the behavior of IV in the form
of diacetate (Table 1) is the presence of only two stages
of mass loss on its thermal curve (Fig. 2). The high-
temperature stage corresponds to the thermal decom-
position of the MHC and does not cause any ques-
tions, while the first is observed at temperatures close
to that of the evaporation of bound water (63°C).
However, the enthalpy of the process is many times
higher than this value not only for water but for acids
as well (187 kJ/mol). Nothing of the kind is observed
for trifluoroacetate IV. The formation of acetates IV
apparently favors the formation of a supramolecular
structure based on them, similar to the one described
in [37]. This is also indicated by substantial differences
in the electronic absorption spectra of solutions of IV
With trifluoroacetic acid, the number of HX mole-
cules evaporated from the porphyrinium salts differs
for different MHCs and is equal to 2 in the case of
compounds I and II, and to 1 for III and IV (Table 1).
Porphyrins and their N-substituted analogs are two-
acid bases, while the corroles in the macrocycle have
only one N-base center [21]. Our data show that
despite the formation by corrole III of a dicationic salt
form with the participation of tertiary nitrogen and a
meso-carbon atom in a solution of concentrated tri-
fluoroacetic acid [21], it does not exist in the crystal-
line state, breaking down to N-monocations.
We did not expect that inverted porphyrinoid IV, a
two-acid N-base (which is experimentally in the form
of tautomer a [34]) cleaves (i.e., initially contains) in AcOH and TFA (Fig. 3).
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LIKHONINA et al.
The third stage of the thermal degradation of cat-
A
3
ionic salts of porphyrinoids is associated with the
decomposition of macrocyclic molecules I–IV in an
inert atmosphere, which begins in the temperature
range of 310–470°С. For example, in the case of ace-
tates I and IV, it occurs in the region of the onset of
melting of a solid substance, recorded on the DCC
curve at 421 and 358°С (Table 1, Fig. 1), respectively,
in the form of an acute endo-peak unaccompanied by
a drop in the mass of the sample.
459
464
2
1
821
2
The stability of the macrocycle after the decompo-
sition of the cationic salt is confirmed by the good
agreement between the temperature of the onset of its
decomposition in the salt (tonset3, Table 1) and the tonset
of the individual compound [20, 21, 38]. Only in one
of the studied cases (II) was partial decomposition of
the MHC observed during the destruction of its diac-
etate. The decomposition is explained by the dealkyla-
tion of N-substituted porphyrinoid II, on the ther-
mocurve of which one more stage of mass loss is
recorded at an initial temperature of 198°C, which is
consistent with data in [38]. There is no stage of deal-
kylation with trifluoroacetate II (Table 1).
According to quantum chemical calculations
(DFT, B3LYP, CC-pVDZ basis) performed for ideal-
ized conditions, the interaction between an НnP
ligand and one or two acid molecules is limited by the
formation of H-bonds with high degrees of charge
transfer (up to 0.27 units; Table 2). In [18, 19], calcu-
lations in the considered basis showed good agreement
with experimental values for the acid–base forms of
NH-active macrocycles with electron donor mole-
cules.
Optimizing the geometry of macrocycles I–IV with
one and/or two AcOH and TFA molecules in combi-
nation with their NBO analysis [31] allowed us to
determine the basic geometric characteristics of the
products of acid–base interaction, along with the
energy parameters of these interactions for structures
of similar structure. According to the calculated
energy of interaction of MHC and HX (Eint, kJ/mol,
Table 2), the stability of mono- and di-cation cations
I–IV with TFA increases in series (4) and (5), respec-
tively:
790
1
0
300
400
500
600
700
800
900
λ, nm
Fig. 3. Electronic absorption spectra of compound IV in
(1) acetic and (2) trifluoroacetic acid.
phyrinoids is usually multicenter, especially for cor-
roles (Table 2, Fig. 4).
The results from quantum-chemical studies show
that some stages of protonation of the N-basic centers
of porphyrinoids observed in solution [21, 39] may not
be observed in the calculated data obtained for ideal-
ized conditions where the energy consumption
required for conformational or π-electronic tuning of
the macrocycle is not compensated for by the forma-
tion of new bonds.
For example, weak proton donor AcOH does not
interact with the second N-base center of the mono-
cation of the N-substituted molecule II, closed on one
side of the macrocycle plane by the methyl group and
the acid molecule on the other (Fig. 4a). The stronger
acid (TFA) in this case forms a doubly protonated
form with this macrocycle (Fig. 4b).
A second example is the absence of the C-proton-
ation of corrole III monocations by mesocarbon
atoms under the conditions of quantum-chemical cal-
culations. These results are consistent with the exper-
imental data obtained thermogravimetrically
(Table 1).
According to the calculated data, one likely prod-
uct of the interaction between corrole (III) and the
first carboxylic acid molecule is complex H-bonded
bridge structures, which probably do not form in solu-
tion, and in which the N-center is an acceptor and the
NH-center is a proton donor with respect to acid HX
(Fig. 4c). The hydrogen bonds that form in this case
are characterized by fairly high Estab values of 93 and
78 kJ/mol for AcOH and TFA, respectively (Table 2).
The occurrence of H−X … (H−N) interaction even in
the protonated form of the macrocycle testifies to the
high chemical activity of the NH bonds of the mole-
cules of the initial H3Cor (III).
(4)
(5)
I < II < IVb < III < IVa,
I < II < IVb < IVa.
These series are in agreement with the range of НnР
basicity obtained thermogravimetrically (see above).
At the same time, there is no such agreement when we
compare the thermal analysis data and the energies of
stabilization of individual H bonds (Estab, kJ/mol) and
the charges (qstab, charge unit) transferred during their
formation. This is because Eint reflects the total energy
of porphyrinoid–acid interaction, while Estab rep-
resents the energy of individual orbital interactions.
In the case of tautomer a of inverted porphyrinoid
According to the calculated data, the real ABI of por- (IV), there are two alternative N-centers of protona-
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INTERACTION BETWEEN meso-PHENYL-SUBSTITUTED PORPHIRINIOIDS
(a) (b) (c)
117
Fig. 4. (Color online) Optimized structures of cationic salts II with (a) one HOAc molecule and (b) two TFA molecules, plus
(c) III with TFA molecule.
tion: external and internal. As expected, the formation
2. Modeling the structure of the cationic forms of
of a monocation with the participation of an external compounds I–IV in the ideal gas phase with quan-
cyclic N atom is, according to NBO analysis, more tum-chemical calculations showed that the interac-
favorable. The energy of interaction of an acid proton tion between an НnP ligand and one or two acid mol-
(TFA) with an external N atom (or, in other words, the
ecules is limited by the formation of H-bonds with a
high degree of charge transfer to 0.27 units. The
energy of stabilization of hydrogen bonds (Estab),
308 kJ/mol) is thus considerably higher than the intra- changes in the energy of macroheterocycle–acid
cyclic one (by 231 kJ/mol), and the magnitude of interaction (ΔEint) characterizing the basicity of MHC
charge transfer (0.272 charge unit) is 0.23 units higher.
I–IV were consistent with the enthalpies of evapora-
tion of acid molecules from porphyrinium salts, calcu-
lated from thermogravimetric data.
As a rule, any increase in Estab and qstab is accompanied
by a shortening of the distances (rX↔Y−H, rX↔H
,
Table 2) between the interacting centers.
The formation of protonated forms of macrohet-
erocycles I–IV leads to considerable distortion of the
planar structure, as follows from the values of dihedral
angles between pairs of Cβ atoms (ϕβ−β), nitrogen
atoms of the MHC (ϕN−N), and the angles of rotation
of mesophenyl rings (ϕAr, Table 2). The dipole
moments during the protonation of MHC also grow
considerably, due to the polarization of the molecule,
especially when the proton is attached to the external
cyclic N-atom IVa or the only tertiary N-atom in the
corrole III molecule (Table 2). As in case I, the forma-
tion of the symmetric dicationic form of Н(n+2)Р2+
results in complete depolarization of the molecule
(μ ∼ 0, Table 2).
FUNDING
This work was supported in part by the Russian Science
Foundation, agreement no. 18-73-00217. The work was
done on equipment at the Ivanovo State University of
Chemistry and Technology’s shared resource center.
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Translated by M. Aladina
https://doi.org/10.1021/jo060007k
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 94
No. 1
2020