Stepwise Mechanism of the Rhenium(V) Porphyrin Reaction with Pyridine, and the Chemical Structure of the Donor–Acceptor Complex

Article abstract of DOI:10.1134/S003602441904006X

Abstract: Chemical thermodynamics and UV, visible, IR, ¹H NMR, and mass spectrometry are used to study the complex reaction of (5,15-bis(4'-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphinato) (oxo)(chloro)rhenium(V) (O=Re(Cl)P) with pyridine (Py) and the chemical structure of the product. The nature and stoichiometry of the reaction are established and the quantitative parameters of two-way stepwise reactions are determined during a complex reaction. There is reversible replacement of Cl^– ions by pyridine molecules with constant K₁ of (4.7 ± 1.1) × 10² L/mol and the formation of cationic complex compound [O=Re(Py)P]⁺Cl^– in the first stage. The second stage is the reversible addition of two pyridine molecules ([O=Re(Py)₃P]⁺Cl^–) with constant K₂ = (0.10 ± 0.03) L²/mol². The reaction studied is a model for processes in self-assembling systems based on metalloporphyrins and pyridyl derivatives of carbon nanoforms for the formation of active layers with photoinduced charge separation in hybrid solar cells.

Full text of DOI:10.1134/S003602441904006X

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2019, Vol. 93, No. 4, pp. 703–709. © Pleiades Publishing, Ltd., 2019.
Russian Text © N.G. Bichan, E.N. Ovchenkova, T.N. Lomova, 2019, published in Zhurnal Fizicheskoi Khimii, 2019, Vol. 93, No. 4, pp. 558–564.
STRUCTURE OF MATTER
AND QUANTUM CHEMISTRY
Stepwise Mechanism of the Rhenium(V) Porphyrin Reaction
with Pyridine, and the Chemical Structure
of the Donor–Acceptor Complex
N. G. Bichana, E. N. Ovchenkovaa, and T. N. Lomovaa,*
a Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, 153045 Russia
*е-mail: tnl@isc-ras.ru
Received July 19, 2018; revised July 19, 2018; accepted July 19, 2018
1
Abstract—Chemical thermodynamics and UV, visible, IR, H NMR, and mass spectrometry are used to
study the complex reaction of (5,15-bis(4'-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethyl-
porphinato) (oxo)(chloro)rhenium(V) (O=Re(Cl)P) with pyridine (Py) and the chemical structure of the
product. The nature and stoichiometry of the reaction are established and the quantitative parameters of two-
way stepwise reactions are determined during a complex reaction. There is reversible replacement of Cl– ions
by pyridine molecules with constant K1 of (4.7 1.1) × 102 L/mol and the formation of cationic complex
compound [O=Re(Py)P]+Cl– in the first stage. The second stage is the reversible addition of two pyridine
molecules ([O=Re(Py)3P]+Cl–) with constant K2 = (0.10 0.03) L2/mol2. The reaction studied is a model
for processes in self-assembling systems based on metalloporphyrins and pyridyl derivatives of carbon nano-
forms for the formation of active layers with photoinduced charge separation in hybrid solar cells.
Keywords: substituted rhenium(V) porphyrin, pyridine, donor–acceptor system, thermodynamics of the for-
mation, chemical structure, spectral properties
DOI: 10.1134/S003602441904006X
INTRODUCTION
with peroxo-coordinated oxygen [15, 16, 18]. The pos-
sibility of varying the axial group in equatorial macro-
cyclic rhenium complexes makes them promising for
use in sensorics [19], catalysis [13], and photodynamic
therapy, where rhenium compounds have already been
tested and proven [20, 21]. The study of substitution
and addition reactions of various groups along the
axial axis of highly charged rhenium oxoporphyrin
complexes considerably affects their main spectral
characteristics, their stability over Re–N bonds [22],
and their ability to form π-cation radicals and inter-
act with molecular oxygen [10, 15]. Further develop-
ment of the indicated areas of rhenium chemistry
requires study of the physical chemistry of its com-
pounds, particularly the reactivity to different sub-
strates and the mechanisms of complex reactions
with their participation.
Organometallic compounds with M–O and M–N
bonds attract much attention as active intermediate
compounds in biologically important reactions [1, 2],
and have been successfully used as effective catalysts in
many industrial processes [3, 4]. The high state of oxi-
dation of the metal in the catalyst allows the reaction
to be conducted under the conditions of open flasks,
without the need for the strict exclusion of air and
moisture [5]. The rich coordination chemistry of rhe-
nium is used in designing radiopharmaceuticals [6–
8], since its isotopes 186Re and 188Re emit radiation.
Rhenium is also widely used as a nonradioactive tech-
netium model in nuclear medicine [9].
The synthesis, properties, and use of rhenium
compounds with carbenes [10], heterocyclic mole-
cules [5, 11, 12], calixarenes [6], and porphyrins [10,
13–15] are described in literature. The different possi-
bilities of modifying rhenium compounds make them
promising platforms for the formation of supramolec-
The aim of this work was to study the reactions
between (5,15-bis(4'-methoxyphenyl)-3,7,13,17-tetra-
methyl-2,8,12,18-tetraethylporphinato)(oxo)(chloro)
ular [16, 17], μ-oxodimeric systems and complexes rhenium(V) (O=Re(Cl)P)
703

704
BICHAN et al.
Me
O
Et
Et
MeO
N
Re
Cl
Me
N
N
Me
N
OMe
Et
Et
Me
and pyridine (Py). The reaction between metallopor-
phyrin (MP) and Py is considered a simple model of
self-assembly in donor-acceptor systems based on
metalloporphyrins and pyridyl derivatives of such car-
bon nanoforms as fullerenes [23, 24]. Porphyrin–
fullerene supramolecules, as confirmed by experimen-
tal studies on fluorescence quenching and calculations
[25], exhibit the property of photoinduced electron
transfer (PET) and can function as active layers of
hybrid solar cells.
The reaction between O=Re(Cl)P and Py was
studied in dichloromethane using the spectrophoto-
metric method of molar ratios at 298 K. A series of
solutions was prepared in CH2Cl2 with a constant con-
centration of O=Re(Cl)P (2.03 × 10−5 mol/L) and
different pyridine concentrations (8.23 × 10–5–
11.17 mol/L). Equilibrium constants of reactions with
Py (K) were determined using the equation for a three-
component equilibrium system according to the least
squares (LS) method using Microsoft Excel:
A − A / A − A
0 ) (
(
)
0
i
∞
0
K =
EXPERIMENTAL
1 − A − A / A − A
0 ) (
(
)
i
∞
(1)
1
(5,15-Bis(4'-methoxyphenyl)-3,7,13,17-tetramethyl-
2,8,12,18-tetraethylporphinato)(oxo)(chloro)rhenium(V),
O=Re(Cl)P was prepared from (5,15-bis(4'-methoxy-
phenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethyl-
×
,
n

A − A0 
A∞ − A0
CPy − CO0=Re(Cl)P
i




0
porphinato)(oxo)(phenoxy)
rhenium(V)
where
,
is the initial concentration of Py
CPy CO=Re(Cl)P
(O=Re(PhO)P), preliminarily synthesized via the
reaction between H2ReCl6 and the corresponding por-
phyrin according to [26], and by passing gaseous HCl
for 10 min through a solution of it in CH2Cl2. During
this time, the color of the solution changed from
green-yellow to wine red. Porphyrin was synthesized
[27] and provided by Professor A.S. Semeikin. The
(O=Re(Cl)P) yield was close to 100%. The UV–Vis
spectrum (CH2Cl2): λmax, nm (log ε) 687 (3.15), 633
and O=Re(Cl)P in dichloromethane, respectively; А0,
Аi, А∞ are the optical densities at the working wave-
length for rhenium(V) porphyrin, the equilibrium
mixture at a given concentration of Py, and the reac-
tion product. The relative error in determining K did
not exceed 30%. The Py stoichiometric coefficient
(n in Eq. (1)) was determined as slope log(Ii) = f(log CPy),
where Ii is the indicator ratio (Ai − A0)/(A∞ − Ai).
1
(3.48), 526 (3.95), 355 (4.52). The 1H NMR spectrum
(CDCl3), ppm, J, Hz: 10.81 (s, 2H, CHmeso), 8.16
(d, 2H, Hо, J = 8.3); 8.08 (d, 2H, Hо, J = 8.3); 7.73
(q, 1H, Hm, J = 8.3); 7.55 (q, 1H, Hm, J = 7.3); 7.39
(m, 2H, Hm); 4.18 (m, 8Н, –CH2–); 2.76 (t, 12Н,
CH3Et, J = 7.3); 2.20 (s, 6Н, p-OCH3); 1.96 (t, 12Н,
CH3, Me, J = 7.6). The mass spectrum (MALDI
UV–Vis, IR, fluorescent, Н NMR, and mass
spectra were recorded, respectively, on an Agilent
8453 spectrophotometer, and on VERTEX 80v,
Avantes AvaSpec-2048, Bruker AVANCE-500, and
Shimadzu Confidence spectrometers.
RESULTS AND DISCUSSION
TOF), m/z 891.35 [M–Cl]+. The one calculated for
C46H48ReN4O3 was 891.12.
Dichloromethane was chosen as the solvent for
studying the reactions between O=Re(Cl)P and Py, as
it has good dissolving ability and chemical inertness in
relation to this complex. The choice of spectropho-
tometry as the research method was due to the elec-
tronic absorption spectra of porphyrin rhenium(V)
complexes being accurate and sensitive to the change
in axial groups. In [14, 26], electronic absorption
spectra were compared for rhenium(V) porphyrins of
composition O=Re(Cl)P upon a change in covalently
The synthesis and properties of 1'-N-methyl-2'-
(pyridine-4-yl)pyrrolidino[3',4':1,2][60]fullerene were
described in [25].
Analytical grade Py was dried for two days over
KOH granules and then distilled (tboil = 115.3°С). Tol-
uene was dried with potassium hydroxide and distilled
before use (tboil = 110.6°С). The water content was
determined via Fischer titration and did not exceed attached X ligands and a different ratio of the band
0.01%. intensities in the 350–460 nm range and the position
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STEPWISE MECHANISM OF THE RHENIUM(V) PORPHYRIN REACTION
705
(a)
(b)
463
A
A
A463
0.5
0.3
0.1
A526
0.8
0.7
0.175
×4
0.165
0.01 0.03 0.05
0.5
0.2
2
4
6
8 10
~
~ ~
~ ~
CPy, mol/L
~
CPy, mol/L
526
0.2
400
500
600
λ, nm
400
500
600
λ, nm
−5
−5
Fig. 1. Change in the UV–Vis spectrum of O=Re(Cl)P (С
2.03 × 10 mol/L) with pyridine additives of 8.23 × 10 –2.23 ×
O=Re(Cl)P
−2
−2
10 mol/L (а) and 2.23 × 10 –11.17 mol/L (b). Inserts show the corresponding spectrophotometric titration curves obtained at
working wavelengths of (a) 526 and (b) 463 nm.
of the charge transfer band in the region of 440– of the changes in UV–Vis spectrum during titration
550 nm were obtained.
and the data in [14, 28, 29] on the effect of substitut-
ing/attaching axial ligands in oxoporphyrin complexes
O=МV(X)P, where М is W, Mo, or Re:
Figure 1 shows UV–Vis spectrum of O=Re(Cl)P in
dichloromethane–Py mixtures as a function of the Py
concentration at 298 K and corresponding titration
curves. A wide range of Py concentrations (8.23 ×
10−5–11.17 mol/L) was used. Two families of spectral
curves in which the isosbestic points are preserved are
clearly present (Fig. 1). The first series of bands is
observed at СPy = 8.23 × 10−5–2.23 × 10−2 mol/L.
There are minor changes in the spectrum. The optical
density of the charge transfer band at 526 nm is
reduced, a new absorption band appears in the region
of 480 nm, and the intensity of the Soret band at
355 nm falls slightly. The second series of bands at
СPy = 2.23 × 10−2–11.17 mol/L is characterized by
considerable changes in UV–Vis spectrum. Absorp-
tion in the region of 480 nm grows more intensely with
a hypsochromic shift of the maximum to 463 nm, a
new absorption band appears in the region of 405 nm,
and the intensity of the Soret band falls from 0.7 to
0.45 optical density units.
K1
←⎯
⎯→
(2)
O=Re(Cl)P + Py
O=Re(Cl)(Py)P.
The second stage (at a Py concentration of 2.23 ×
10−2–11.17 mol/L) is characterized by needing 10–
15 min to reach equilibrium with a much lower K2
constant of (0.10 0.03) L2/mol2 and a stoichiometric
O=Re(Cl)P : Py ratio of 1 : 2 (Fig. 1b):
K2
+
–
⎯⎯→
←⎯⎯
(3)
O=Re(Py) P Cl .
O=Re(Cl)(Py)P + 2Py
[
]
3
The (3) reaction product structure is confirmed by
the IR and 1Н NMR spectroscopy data given below.
The axial bonding is known to have a considerable
effect on the vibrational frequencies of metallopor-
logCPy
−4
−3
−2
−1
0
1
The presence of isosbestic points in both series of
curves, the titration results within each of the series,
and the study of trends in UV–Vis spectra upon dilut-
ing solutions with pyridine show the reaction between
O=Re(Cl)P and Py in dichloromethane proceeds in
two reversible stages.
Analysis of the logI–log CPy dependences (Fig. 2)
allows us to determine the number of Py molecules
that participate in equilibrium. For the first stage (at a
Py concentration of 8.23 × 10−5–2.23 × 10−2 mol/L),
the equilibrium in which is established immediately
after mixing the solutions of O=Re(Cl)P and Py, a
stoichiometric O=Re(Cl)P : Py ratio of 1 : 1 and an
equilibrium constant K1 of (4.7 1.1) × 102 L/mol are
determined, allowing us to write the left-hand side of
equilibrium (2). The right-hand side is written in light
1.5
1
−0.5
2
−2.5
logI
Fig. 2. Dependences of log I on log C for the reaction
between O=Re(Cl)P and pyridine additives of (1) 8.23 ×
10 –2.23 × 10 mol/L (R = 0.97, tanα = 0.91) and
(2) 2.23 × 10 –11.17 mol/L (R = 0.98, tanα = 2.09) at
Py
−5
−2
2
−2
2
298 K.
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706
BICHAN et al.
Table 1. IR spectra in KBr
ν, сm−1
plane [23]. This is also indicated by the high-fre-
quency shift of ν(Re–N) by 5 cm−1. The vibrations of
peripheral macrocycle substituents (phenyl and alkyl
groups) are practically unchanged (Table 1).
Bands
assingment
[O=Re(Py)3P]+ ⋅ Cl–
O=Re(Cl)P Py
New signals of coordinated Py at 2963, 2930, 1637,
1487, 1398, 1174, and 698 cm−1 missing in the spec-
trum of the initial complex and shifting by 4–40 cm−1
relative to the vibrations of pure Py (Table 1) are
observed in the IR spectrum of the reaction (3) prod-
uct, [O=Re(Py)3P]+Cl−. The new signal at 542 cm−1
presumably corresponds to Re–NPy bonds [30]. The
3065
3030
ν(C–H)Ph
ν(С–Н)Py
3031
2963
2930
2871
2854
1637
2956
2910
2873
2856
ν(C–H) alkyl
groups
Py ring
vibrations
signal at 962 cm−1 corresponding to ν(Re=O) in the
IR spectrum of the product confirms the chemical
nature of [O=Re(Py)3P]+Cl−.
1633
1581
1608
1570
1512
1482
1460
1609
1571
1512
1487
1455
1441
1398
1378
ν(C=C)
1
O=Re(Cl)P has the Н NMR spectrum typical of
diamagnetic MPs with clearly separated signals and is
in good agreement with the literature data [26]. The
introduction of Py (in the concentration leading to the
formation of [O=Re(Py)3P]+Cl−) into the solution of
O=Re(Cl)P in CDCl3 is accompanied by the emer-
gence of three proton signals of pyridine rings at 8.58,
7.62, and 7.24 ppm, which undergo a slight upfield
shift (0.04–0.06 ppm) relative to the signals of unco-
ordinated pyridine [31]. The axial bonding of Py leads
to an upfield shift (relative to the spectrum of
O=Re(Cl)P in CDCl3) of the signals of the meso-pro-
tons of the macrocycle (by 0.06 ppm) and signals of
the ortho-protons of phenyl substituents (by ≈0.1 ppm),
while the protons of the –OCH3 group are shifted
downfield (by ≈0.1 ppm). Such shifts of the proton sig-
nals of the macrocycle in the composition of the por-
phyrin–pyridine supramolecule [O=Re(Py)3P]+Cl−
can be explained by the reduced effect of the ring cur-
rent of the porphyrin macrocycle due to the emer-
gence of an additional positive charge on the Re atom
upon adding Py molecules.
ν(С–N)Py
ν(C=N)
δ(C–H)
ν(С–N)Py
ν(C–N)
δ(C–H)
methyne groups
ν(С–Н)Py
δ(C–H)
1441
1438
1379
1290
1249
1288
1245
1174
1217
1147
110 4
1058
110 4
1069
1031
991
δ(С–Н)Py
1026
982
963
826
846
790
749
723
ν(Cβ–С)
alkyl groups
ν(Re=O)
γ(C–H)
981
962
A comparison of equilibrium constants K1 and K2
shows that the presence of one Py molecule in the
O=Re(Cl)(Py)P first coordination sphere prevents
the subsequent bonding of Py in the second stage of
the process. The displacement of Cl− from the
O=Re(Cl)(Py)P coordination sphere and the addition
of two more Py molecules occur over time.
During the reaction between O=Re(Cl)P and Py,
two pyridine-containing compounds of rhenium(V)
porphyrin, O=Re(Cl)(Py)P and [O=Re(Py)3P]+Cl−
can be separated from the solution, the electronic
absorption spectra for which differ in the position of
the bands and the ratio of their intensities. The UV–
790
750
720
748
704
603
δ(С–Н)Py
698
542
471
ν(Re–NPy)
ν(Re–N)
ν(Re–Cl)
464
379
Vis spectrum of O=Re(Cl)(Py)P in CH2Cl2 (λmax
,
nm) are (I) 353, 484 (shoulder) and (II) 518 (II > I).
phyrin molecules [23]. Upon adding three Py mole-
cules to O=Re(Cl)P, the largest changes (low-fre- For [O=Re(Py)3P]+Cl–, (I) 409, (II) 461, and (III)
quency shifts of 2–5 cm−1) display skeletal vibrations
of the macrocycle (ν(C=N), δ(C–H) of methyne
groups), which is logically associated with the change
545 (II > I > III).
A comparison of the properties of the donor–
acceptor system obtained and analogs based on oxo-
in the positions of metal atoms in the macrocycle porphyrin complexes with different sets of substituents
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STEPWISE MECHANISM OF THE RHENIUM(V) PORPHYRIN REACTION
707
Table 2. Quantitative parameters of the reactions between metalloporphyrins and pyridine in toluene
Kn, L/mol
Reaction equation
Source
K1
⎯⎯→
←⎯⎯
O=Re(Cl)P + Py
O=Re(Cl)(Py)P
(4.7 1.1) × 102
(0.10 0.03) L2/mol2
(1.33 0.22) × 104
(8.42 1.58) × 103
89 13
K2
+
−
⎯⎯→
←⎯⎯
O=Re(Cl)(Py)P + 2Py
[O=Re(Py)3P] Cl
K1
⎯⎯→
O=W(OH)TPP + Py
O=W(OH)(Py)TPP
[25]
←⎯⎯
K2
+
−
⎯⎯→
O=W(OH)(Py)TPP + Py
[O=W(Py)2TPP] OH
''
←⎯⎯
K3
+
-
[O=W(Py) TPP] OH + Py + H O
[(OH)W(Py) TPP]2+ 2OH−
''
[26]
''
⎯⎯→
←⎯⎯
2
2
3
K1
+
–
(9.1 1.2) × 103
⎯⎯→
←⎯⎯
O=Mo(OH)TPP + Py
[O=Mo(Py)TPP] OH
K2
+
–
+
–
⎯⎯→
K3
[O=Mo(Py)TPP] OH + Py + H O
[(OH)Mo(Py)2TPP] 2OH
[Mo(Py) TPP]3+ 3OH–
39.3 5.2
←⎯⎯
2
+
–
⎯⎯→
[(OH)Mo(Py) TPP] 2OH + Py
1.0 0.1
''
←⎯⎯
2
3
K is a stepwise equilibrium constant.
n
and central metal atoms earlier studied (Table 2) ligand in the external coordination sphere was studied
shows that the porphyrin–pyridine complexes were qualitatively. Such porphyrin–fullerene dyads have
relatively stable. It can be seen from Table 2 that the the property of electron transfer from a donor (macro-
reaction between oxo-coordinated MP (M = Re, W, cycle) to an acceptor (fullerene fragment) during pho-
Mo) and Py is a complex process which ends with the toexcitation. For fluorescent metalloporphyrins
formation of donor–acceptor complexes with a stoi- (manganese(III), molybdenum(V), and other com-
chiometric composition of 1 : 3 in all cases. The reac- plexes), PET is detected from fluorescence quenching
tion of O=Re(Cl)P is characterized by lower values of upon the formation of the donor–acceptor complex
the equilibrium constants than the similar reactions of [25, 33]. Preliminary testing of the rhenium
O=W(OH)TPP and O=Mo(OH)TPP. The sequence O=Re(Cl)P complex for coordination ability with
of the change in K values repeats the series of changes respect to acceptor 1'-N-methyl-2'-(pyridine-4-
in the covalent radius of W (162 pm), Mo (154 pm), yl)pyrrolidino[3',4':1,2][60]fullerene (PyC60)
and Re (151 pm) [32]. However, this correlation could
CH3
N
be random, since the nature of the stepwise reactions
between MP and Py changes dramatically. With
Mo‒W complexes, if the O=Re(Cl)P reaction with Py
does not affect the oxo group in the molecule, the lat-
ter becomes the center of the reaction in the second
and third stages of the reaction with Py, respectively.
The established relationship between the stability con-
stants of the porphyrin–pyridine supramolecules and
the nature of the metal of the porphyrin component of
the donor–acceptor complex can be used in develop-
ing and synthesizing donor-acceptor systems with pre-
dictable stability. This is an important factor in opti-
mizing the chemical structures of compounds to cre-
ate hybrid materials based on them (e.g., catalytic
systems, sensors, and photoactive components for
photovoltaic devices).
The formation of a stable donor–acceptor com-
pound of rhenium(V) porphyrin with the first Py mol-
ecule indicates the obtained data can be used to create
donor–acceptor dyads of metalloporphyrins with pyr-
idyl derivatives of nanocarbon. In [16], the self-orga-
nization of 5-phenyl-2,3,7,8,12,13,17,18-octaethyl-
porphinato)(oxo)(phenoxo)rhenium(V)–2'-(pyridine-
4-yl)-5'-(pyridine-2-yl)-1'-(pyridine-3-ylmethyl)-2',4'-
dihydro-1'H-pyrrolo[3',4':1,2][С60-Ih][5,6]fullerene–
dichloromethane systems ending in the formation of a
N
using electronic absorption and fluorescence spec-
troscopy had a positive result namely the formation of
donor-acceptor porphyrin-fullerene in the CH2Cl2
medium. Despite less pronounced changes in the
UV–Vis spectrum of O=Re(Cl)P with an excess of
substituted fullerene instead of pyridine (i.e., a slight
increase in the intensity of the band at 355 nm and a
hypsochromic shift of the charge transfer band to 524
nm; Fig. 3a), the formation of a donor-acceptor com-
plex and charge redistribution in it can be identified
from the considerable drop in the fluorescence of free
substituted fullerene, compared to the metalloporphy-
rin-bound fullerene (Fig. 3b).
The results [25, 34] from modifying titanium pho-
toanodes with films of donor–acceptor complexes
cationic donor–acceptor 1 : 1 complex with a PhO− based on d-metals (including rhenium) that show an
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BICHAN et al.
A
I
(a)
(b)
×4
0.6
500
250
~ ~ ~
~ ~ ~
3
0.2
2
2
1
1
400
600
800 λ, nm
700
800
λ, nm
Fig. 3. (a) Electronic absorption and (b) fluorescence spectra recorded in dichloromethane at 298 K of (1) O=Re(Cl)P, (2) its
−5
−5
complex with PyС , and (3) PyС ; (1, 2) С
= 2.13 × 10 mol/L; (2, 3)
= 8.32 × 10 mol/L; λ = (1, 2) 525
PyC60
exc
C
60
60
O=Re(Cl)P
and (3) 395 nm.
11. C. Shi and G. Jia, Coord. Chem. Rev. 257, 666 (2013).
increase in the conversion of light energy in the pres-
ence of modifiers are an additional argument in favor
of extending the possibilities of designing photoactive
supramolecules using rhenium(V) porphyrins.
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ACKNOWLEDGMENTS
14. N. G. Bichan, E. Yu. Tyulyaeva, I. A. Khodov, and
T. N. Lomova, J. Mol. Struct. 1061, 82 (2014).
This work was performed on equipment at the
shared resource center of the upper Volga region cen-
tre of physicochemical research. Fluorescence spectra
were taken by Yu.A. Gubarev, PhD, to whom we are
grateful. Our synthesis of pyrrolidinyl[60]fullerene was
supported by the Russian Foundation for Basic
Research, project no. 16-03-00578.
15. N. G. Bichan, E. Yu. Tyulyaeva, and T. N. Lomova,
Russ. J. Inorg. Chem. 59, 1445 (2014).
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