Synthesis of Cyclometalated Platinum(II) Complex with an Alkynyl-Substituted Isocyanide Ligand, Its Structure and Photophysical Properties

Article abstract of DOI:10.1134/S1070363220040143

Abstract: The cyclometalated complex of platinum(II) [Pt(ppy)Cl(CNC₆H₄CCPh)] with phenylpyridine and [4-(2-phenylethynyl)phenyl]isocyanide ligands has been synthesized from the [Pt(ppy)Cl]₂ dimer and CNC₆H₄

Full text of DOI:10.1134/S1070363220040143

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 4, pp. 648–654. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 4, pp. 591–598.
Synthesis of Cyclometalated Platinum(II) Complex
with an Alkynyl-Substituted Isocyanide Ligand, Its Structure
and Photophysical Properties
S. A. Katkovaa,*, A. A. Leshcheva, A. S. Mikherdova, and M. A. Kinzhalova
a St. Petersburg State University, St. Petersburg, 199034 Russia
*e-mail: s.katkova@spbu.ru
Received October 17, 2019; revised October 17, 2019; accepted October 21, 2019
Abstract—The cyclometalated complex of platinum(II) [Pt(ppy)Cl(CNC6H4CCPh)] with phenylpyridine and
[4-(2-phenylethynyl)phenyl]isocyanide ligands has been synthesized from the [Pt(ppy)Cl]2 dimer and CNC6H4C-
CPh isocyanide with 90% yield. The compound structure has been characterized using mass spectrometry, IR
and NMR spectroscopy methods as well as single-crystal X-ray diffraction. The photophysical properties of the
complex in a solid phase have been studied.
Keywords: platinum complexes, isocyanides, luminescence
DOI: 10.1134/S1070363220040143
The C,N-cyclometalated platinum(II) complexes are
among the most promising organometallic luminophores,
displaying the room-temperature luminescence over
the entire visible light range [1–3]. They exhibit
high efficiency for the photophysical processes of
intercombination conversion of the excite singlet state
into the lower-energy triplet state, resulting in the efficient
phosphorescence [2]. The luminophores based on the
heteroleptic C,N-cyclometalated platinum(II) complexes,
[Pt(C^N)(L,L')]z, are the most interesting, since they can
emit light over the entire visible range, the wavelength
being tuned via the variation of the cyclometalating (C^N)
and auxiliary (L, L') ligands [1–3]. The introduction of
strong σ-donating ligands (for instance, isocyanides) in the
luminophore molecule leads to the increase in the energy
difference between HOMO and LUMO levels of the
complex and thus to hypsochromic shift of the emission
to blue range, affording the luminophores exhibiting high
quantum yield [3]. Linear geometry of the isocyanide and
the absence of steric hindrance facilitate the formation of
the metallophilic Pt···Pt interactions and the π–π-stacking
which enhance the structural rigidity of the molecules,
thus reducing the radiationless energy scattering [4, 5].
Certain cyclometalated platinum(II) complexes with
isocyanide ligands exhibiting promising photophysical
[1, 6–8] and photocatalytic [9–11] properties have been
described, yet the range of the isocyanide ligands used in
these studies has been limited. It should be underscored
that the C,N-cyclometalated platinum(II) complexes
containing one halide and one isocyanide group as the
auxiliary ligands have been extremely scarce [5, 12–15];
such complexes for cyclometalated 2-phenylpyridine
have not been mentioned.
Moreover, the isocyanide ligands can be involved in
the nonvalent interactions [9–22] which allow the tuning
of photophysical parameters of the luminescent materials.
The low energy of such interactions makes the involved
processes reversible, fast, and readily tunable [23–26].
In this regard, the presence of a lengthy system of the
conjugated bonds and the absence of bulky substituents
are the key factors in the choice of the isocyanide ligand.
Herein we investigated the preparation of such complexes
exemplified by compound 6containing 4-(phenylethynyl)-
phenyl substituent (Scheme 1).
Isocyanide 4 was synthesized via synthetic Scheme 1.
Formamide 3 was prepared from 4-iodoaniline 1 in
two stages involving the formation of formamide 2 and
its Sonogashira cross-coupling with phenylacetylene.
The addition of equimolar amount of compound 4
to a suspension of the chloride-bridged dimer 5 in
1,2-dichloroethane followed by 2 h refluxing afforded
648

SYNTHESIS OF CYCLOMETALATED PLATINUM(II) COMPLEX
649
Scheme 1.
the [Pt(ppy)Cl(CNC6H4CCPh)] complex 6 in good yield
(90%).
isocyanide group at 131.1 ppm was weak, which was
typical of such complexes [27, 32, 33]. Furthermore, the
13С NMR signals at 87.8 and 93.0 ppm were assigned to
the carbon atoms at the triple С≡С bond. The platinum
atom signal in the 195Pt NMR spectrum of complex 6
was found at –3880 ppm, being typical of the isocyanide
platinum(II) complexes [27, 32, 33].
Complex 6 was isolated as light yellow crystalline
solid (decomposing at 171°С) and characterized by
means of mass spectrometry as well as IR and NMR
spectroscopy. Its solid-state structure was elucidated by
single-crystal X-ray diffraction (Fig. 1).
The solid-state structure of complex 6 was elucidated
by means of single-crystal X-ray diffraction (Fig. 1).
The values of the selected bond lengths and angles are
collected in Table 1.
Mass spectrum of complex 6 contained the strongest
peak assigned to the [M – Cl]+ ion with the characteristic
isotopic distribution. The IR spectrum of the complex
contained a strong band of the C≡N bond stretching at
2176 cm–1, being in good agreement with the reference
data on isocyanide complexes of platinum [27–29].
Moreover, the following bands were observed: С–H
stretching (3054 cm–1), C–C ring deformation (1604,
1502 cm–1), С–H in-plane deformation (1066 cm–1), and
С–H out-of-plane deformation (841, 756, 689 cm–1).
1H NMR spectrum of complex 6 contained a set
of signals in the spectral range typical of the aromatic
protons, assignable to those of the ppy and isocyanide
fragments. A distinctive high-frequency signal at
9.58 ppm was assigned to the H11 proton (see the
enumeration in Fig. 1) of the ppy group, the downfield
shift being due to its strong deshielding by the nitrogen
atom [30, 31]. The signal multiplicity was owing to the
splitting at the 195Pt nucleus [30, 31]. The 13С NMR
spectrum revealed that the signals of the carbon atoms
nearest to the platinum atom (С1, С7, С11) were also split
at the 195Pt nucleus. The signal of the carbon atom of the
The crystallographically independent part of structure
6 was represented by a single [Pt(ppy)Cl(CNC6H4CCPh)]
molecule (Fig. 1). The carbon atoms of the phenylpyridine
and isocyanide moieties coordinated to platinum(II)
were in the cis configuration. The platinum–carbon bond
of the isocyanide fragment was 0.1 Å shorter than that
with the carbon atom of the cyclometalated ligand. Other
bond lengths were in good agreement with the known
Fig. 1. General view of a molecule of complex 6 in the crystal
(CCDC 1956173).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 4 2020

650
KATKOVA et al.
Table 1. Selected bond lengths and angles in complex 6
and emission spectra were recorded, and the excited state
lifetime was measured.
Bond length
Pt1–Cl1
Pt1–N1
d, Å
Angle
φ,deg
The absorption spectrum of complex 6 (Fig. 2)
contained a strong band at λ = 350 nm which could be
assigned to the intraligand π–π*-transitions. The weaker
bands at λ = 410 nm were likely due to the intraligand
charge transfer (1ILCT) [ppy, π→π*], the ligand to ligand
charge transfer [1LL0CT (L = ppy, L0 = CNC6H4CCPh)],
and the metal to ligand charge transfer (1MLCT)
[dσ*(Pt)→(π*, ppy)] as well as the mixed-ligand charge
transfer 1MLCT/1ML0CT. The observed bands practically
coincided with the positions of the corresponding bands
for other similar monoisocyanide complexes [M(C^N)
Cl(CNR)] [5–7, 12].
2.388(1)
2.055(3)
1.997(4)
1.888(4)
1.150(5)
1.203(6)
C1Pt1N1
80.97(15)
89.85(34)
169.5(4)
179.1(4)
176.6(5)
176.9(5)
C12Pt1Cl1
C12N2C13
N2C12Pt1
C19C20C21
C20C19C16
Pt1–C1
Pt1–C12
N2–C12
C20–C19
interatomic distances in isocyanide platinum(II) and
palladium(II) complexes [27, 32, 33].
The metallophilic Pt···Pt interactions typical of
bis-isocyanide platinum(II) complexes [35] were not
observed in the structure of complex 6. To elucidate the
interatomic contacts contributing to the crystal packing,
we performed the Hirshfeld surface analysis for structure
6 [36]. The following fractional contributions of the
interatomic contacts were revealed (%): C–H 37.4, H–H
35.9, Cl–H 9.0, C–C 7.1, N–H 3.4, Pt–H 2.3, C–N 1.8,
C–Cl 1.4, Pt–C 1.0, and N–Cl 0.7. Hence, the Hirshfeld
surface analysis of structure 6 showed that the interatomic
interactions involving hydrogen atoms determined the
crystal packing of the compound. However, the presence
of the C–C and C–N contacts between the atoms involved
in the π–π-interactions as well as the contacts with the
platinum atoms which could affect the photophysical
properties of the complex should be underestimated.
In the red part of the spectrum contained a low
absorption band at λ = 480 nm which could be assigned
to the spin-allowed charge transfer from the metal–metal–
ligand bond (1MMLCT) due to the [dσ*(Pt)2→(π*, ppy)]
and [σ*(π, ppy)→σ(π*, ppy) transfer [7, 8, 37]. Therefore,
the presence of that band pointed at the interaction with
the platinum atom and the π–π-interactions.
The emission spectrum of complex 6 revealed
vibrationally structured with maximum of emission,
which was in agreement with the corresponding data for
the [M(C^N)Cl(CNR)] monoisocyanide complexes [7, 15,
38]. The bands at λ = 485, 519, and 560 nm were due to the
transfers assigned to the cyclometalated ppy ligand (3IL
and 3ILCT) as well as to the mixed-ligand contribution
3
owing to the MLCT/3ML0CT tranfer (L = ppy, L0 =
3
CNC6H4CCPh). The contribution from the MMLCT
transfers led to the appearance of an additional band at
λ = 650 nm and the shift of the bands to the long-wave
part.
The photophysical properties of the prepared complex
6 in a solid state were investigated (Fig. 2): the absorption
The lifetime of the excited state of complex 6 was of
the microsecond range (0.8 μs), evidencing the triplet
nature of the excited state [5, 37].
In summary, the possibility of the preparation of
cyclometalated platinum(II) complexes containing
arylisocyanide with the extended conjugation chain as
one of the auxiliary ligands was demonstrated using the
[Pt(ppy)Cl(CNC6H4CCPh)] complex as the example.
EXPERIMENTAL
The starting chemicals and solvents were purchased
fromAldrich and used as received, except for 1,2-dichloro-
ethane, CH2Cl2, THF, and Et2O. 1,2-Dichloroethane
and CH2Cl2 were distilled over P2O5, THF was distilled
over CaO, and Et2O was distilled over sodium metal in
Ȝ, nm
Fig. 2. Absorption (1) and emission (2) spectra of complex 6
in solid state (293 K).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 4 2020

SYNTHESIS OF CYCLOMETALATED PLATINUM(II) COMPLEX
651
the presence of benzophenone. The chlorine-bridged
complex 5 was prepared from K2[PtCl4] as described
elsewhere [30].
7.06 d (1H,ArH, 3JHH = 8.5 Hz), 7.33–7.38 m (3H,ArH),
7.50–7.56 m (5H, ArH), 8.40 s (1H, NH), 8.75 d (1H,
HCO, 3JHH = 11.3 Hz), 8.39 br. s (1H, NH), 8.65–8.67 m
(1H, HCO).
Mass spectrometry analysis was performed using
a Bruker micrOTOF instrument (Bruker Daltonics)
in the electrospray ionization mode with methanol as
solvent. The m/z values were reported for the strongest
signals of the isotopologs. IR spectra were recorded
using a Shimadzu FTIR 8400S spectrometer (4000–
1-Isocyano-4-[(2-phenyl)ethynyl]benzene (4)
[40]. A mixture of 0.3 g (1.36 mmol) of formamide 3 in
10 mLof distilled CH2Cl2 was cooled to –10°С and stirred
during 15 min under argon; 0.62 mL (0.4 g, 11.9 mmol)
of triethylamine and then 0.14 mL (230 mg, 1.5 mmol)
of POCl3 (dropwise over 1 h) were added. The obtained
mixture was stirred during 2 h at –10 to 0°С; after that,
a solution of sodium hydrocarbonate was added, and the
mixture was stirred during 10 min at room temperature.
The organic layer was separated, washed with CH2Cl2
(3×50 mL), and dried over anhydrous MgSO4. The
solvent was evaporated under vacuum, and the residue
was purified via chromatography on silica gel [eluent:
hexane–ethyl acetate (5 : 1)]. Yield 194 mg (70%). IR
1
400 cm–1, KBr pellets). H, 13С{1H}, and 195Pt{1H}
NMR spectra of the solutions in СDCl3 were recorded
using a Bruker Avance II+ spectrometer [400.13 (1Н),
100.61 (13C), and 86 MHz (195Pt)] at room temperature.
Absorption spectra were recorded using a UV-1800
spectrophotometer. Excitation and emission spectra as
well as the luminescence lifetime were studied using
a Fluorolog-3 spectrofluorimeter (Horiba Jobin Yvon).
N-(4-Iodophenyl)formamide (2) [39]. ZnO (2.754 g,
0.034 mol) was added portionwise to 45 mLof 85% formic
acid (54.9 g, 1.2 mol) at cooling. The obtained suspension
was stirred during 15 min, and then 4-iodoaniline (15 g,
68 mmol) was added. The mixture was heated at 75°С
during 2 h until the conversion of the starting aniline was
complete (TLC monitoring). The mixture was cooled to
room temperature, diluted with 100 mL of CH2Cl2, and
filtered to remove ZnO. The filtrate was washed with
saturated solution of sodium hydrocarbonate to neutral
reaction of the medium. The organic layer was dried over
anhydrous MgSO4 and concentrated under vacuum; the
residue was purified via chromatography on silica gel
[eluent: hexane–ethyl acetate (1 : 1)]. Yield 13.4 g (80%).
1H NMR spectrum (СDCl3), δ, ppm: 6.85 d (1H, ArH,
3JHH = 8.6 Hz), 7.33 m (1H,ArH), 7.63–7.68 m (2H,ArH),
8.39 s (1H, NH), 8.65–8.70 m (1H, HCO).
1
spectrum, ν, cm–1: 2125 (N≡C). H NMR spectrum
(СDCl3), δ, ppm: 7.35–7.38 m (4Н, ArH), 7.52–7.55 m
(5Н,ArH). 13С NMR spectrum (СDCl3), δC, ppm: 126.46
(C≡N), 92.20, 87.31 (C≡C); 132.56, 131.70, 128.88,
128.47, 124.82, 122.49 (CAr).
[Pt(ppy)Cl(CNC6H4CCPh)] (6). A solution of
isocyanide 4 (53 mg, 0.26 mmol) in 10 mL of
1,2-dichloroethane was added dropwise over 1 h to a
suspension of [Pt(ppy)Cl]2 (100 mg, 0.13 mmol) in
20 mL of 1,2-dichloroethane at stirring and heating to
50°С. The obtained mixture was stirred at 80°С during
2 h and evaporated to minimal volume; 10 mL of Et2O
was then added. The precipitate was separated off and
recrystallized from a CH2Cl2–Et2O mixture (2 : 1).
Yield 138 mg (90%), decomp. 171°С. IR spectrum, ν,
cm–1: 2176 (N≡C). 1H NMR spectrum (СDCl3), δ, ppm:
7.13 t. d (1H, H3, ppy, 3JHH = 6.7, 1.3 Hz), 7.19 t. d (1H,
N-{4-[(2-Phenyl)ethynyl]phenyl}formamide (3)
[40]. A mixture of 47 mg (0.21 mmol) of Pd(OAc)2,
118 mg (0.45 mmol) of PPh3, 44 mg (0.73 mmol) of
CuI, and 10 mL of THF was stirred during 30 min
under argon atmosphere, and then 1.15 g (4.7 mmol)
of N-(4-iodophenyl)formamide 2, 0.51 g (5 mmol) of
phenylacetylene, and 0.10 g (10 mmol) of triethylamine
were added in sequence. The reaction mixture was stirred
at 60°С during 4–6 h. After the reaction was complete,
the mixture was cooled to room temperature, filtered
through celite, and washed with CH2Cl2 (3×50 mL). The
solvent was evaporated off; the product was isolated via
recrystallization from methanol and dried under vacuum.
Yield 0.61 g (59%). 1H NMR spectrum (СDCl3), δ, ppm:
H4, ppy, 3JHH = 7.4, 0.9 Hz), 7.31 t (1H, H10, ppy, 3JHH
=
6.1 Hz), 7.37–7.39 m (3H, C≡СC6H4), 7.59–7.52 m
(5.5H, C6H4C≡СC6H4 + H2 + H5, ppy), 7.61–7.3 m (2H,
C≡NC6H4), 7.73–7.77 m (1H, H8, ppy), 7.90 t. d (1H,
H9, ppy, 3JHH = 7.8, 1.3 Hz), 9.58 d (1H, H11, ppy, 3JHH
=
5.0, JPtH = 28.5 Hz). 13С NMR spectrum (СDCl3), δС,
ppm: 87.78, 92.96 (C≡С), 118.57 (C8, ppy), 122.26
(C10,ppy), 122.42 (C6H4C≡СC6H4), 124.24 (C5), 124.77
(C4), 125.56, 126.56, 128.50, 128.99 (C6H4C≡СC6H4),
131.14 (C≡N), 131.50 (C3, ppy), 131.75 and 132.83
(C6H4C≡СC6H4), 136.16 (С2, ppy), 140.31 (C9, ppy),
141.39 (С1, ppy), 144.02 (C6, ppy), 148.99 (C11, ppy),
166.39 (C7, ppy). 195Pt{1H} NMR spectrum (СDCl3):
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 4 2020

652
KATKOVA et al.
δPt –3880 ppm. Mass spectrum, m/z: 552.0992 [M – Cl]+
REFERENCES
(calculated for C26H17N2Pt+: 552.1036).
1. Chen, Y., Lu, W., and Che, C.M., Organometallics,
2013, vol. 32, p. 350.
X-ray diffraction analysis of complex 6 was
performed using an Xcalibur, Eos diffractometer.
The measurement was performed at 100 K using
monochromatic MoKα radiation (λ = 0.71073 nm). The
unit cell parameters were refined via least squares method
basing on 35525 reflections with 2θ 5.186–54.996°. The
structure was solved via direct methods and refined to R1 =
0.0271 (wR2 = 0.0669) over 4652 independent reflections
with |Fo| ≥ 4σF using SHELX software [41, 42] available
in OLEX2 package [43]. Empirical correction for
absorption was performed using CrysAlisPro software
package via spherical harmonics implemented in the
SCALE3 ABSPACK scaling algorithm [44].
https://doi.org/10.1021/om300965b
2. Li, K., Tong, G.S.M., Wan, Q.Y., Cheng, G., Tong, W.Y.,
Ang, W.H., Kwong, W.L., and Che, C.M., Chem. Sci.,
2016, vol. 7, p. 1653.
https://doi.org/10.1039/C5SC03766B
3. Chi, Y. and Chou, P.T., Chem. Soc. Rev., 2010,
vol. 39, p. 638.
https://doi.org/10.1039/b916237b
4. Solomatina, A.I., Krupenya, D.V., Gurzhiy, V.V.,
Zlatkin, I., Pushkarev, A.P., Bochkarev, M.N., Bes-
ley, N.A., Bichoutskaia, E., and Tunik, S.P., Dalton
Trans., 2015, vol. 44, p. 7152.
https://doi.org/10.1039/c4dt03106g
Complex 6. C26H17ClN2Pt, M = 587.95, monoclinic
crystal system, space group P21/c, a = 18. 3454(4) Å, b =
5. 34210(10) Å, c = 22. 22.1852(4) Å, β = 110.499(2)°,
V = 2036.54[38] Å3, Z = 4, dcalc = 1.918 g/cm3, μ =
7.037 mm‒1, 4652 independent reflections with I > 2σ(I),
R1(|Fo| ≥ 4σF)/R1 (over all data) = 0.0271/0.0313, wR2
(|Fo| ≥ 4σF)/wR2 (over all data) = 0.0669/0.0699, S =
1.054, ρmin/ρmax = 1.39/‒1.63 e/Å3.
5. Solomatina, A.I., Aleksandrova, I.O., Karttunen, A.J.,
Tunik, S.P., and Koshevoy, I.O., Dalton Trans., 2017,
vol. 46, p. 3895.
https://doi.org/10.1039/c7dt00349h
6. Diez, A., Fornies, J., Fuertes, S., Lalinde, E., Larraz, C.,
Lopez, J.A., Martin, A., Moreno, M.T., and Sicilia, V.,
Organometallics, 2009, vol. 28, p. 1705.
https://doi.org/10.1021/om800845c
7. Fornies, J., Sicilia, V., Borja, P., Casas, J.M., Diez, A.,
Lalinde, E., Larraz, C., Martin, A., and Moreno, M.T.,
Chem. Asian J., 2012, vol. 7, p. 2813.
The Hirshfeld surface analysis of the complex 6 crystal
structure was performed in the frame of normalized
contact lengths (dnorm) [42] based on Bondi van der
Waals radii [45], as implemented in CrystalExplorer 3.1
software.
https://doi.org/10.1002/asia.201200585
8. Shahsavari, H.R., Aghakhanpour, R.B., Hossein-
Abadi, M., Haghighi, M.G., Notash, B., and Fereidoonne-
zhad, M., New J. Chem., 2017, vol. 41, p. 15347.
https://doi.org/10.1039/c7nj03110f
FUNDING
9. Li, Z., Han, Y., Gao, Z., and Wang, F., ACS Catal., 2017,
vol. 7, no. 7, p. 4676.
This study was financially supported by the Russian
Foundation for Basic Research (grant no. 18-03-00119,
synthesis of isocyanide ligand) and the Science Council
of President of RF (grant MK-1476.2019.3, synthesis of
platinum complex and study of its photophysical properties)
and performed using the equipment of the St. Petersburg State
University Resource Centers: Center for Magnetic Resonance,
Center for X-ray Diffraction Studies, Center for Chemical
Analysis and Materials Research, Centre for Optical and Laser
Materials Research, and Chemistry Educational Centre.
https://doi.org/10.1021/acscatal.7b00709
10. Mahmudov, K.T., Kukushkin, V.Y., Gurbanov, A.V., Kin-
zhalov, M.A., Boyarskiy, V.P., da Silva, M.F.C.G., and Pom-
beiro, A.J.L., Coord. Chem. Rev., 2019, vol. 384, p. 65.
https://doi.org/10.1016/j.ccr.2019.01.002
11. Gee, J.C., Fuller, B.A., Lockett, H.-M., Sedghi, G.,
Robertson, C.M., and Luzyanin, K.V., Chem. Comm., 2018,
vol. 54, p. 9450.
CONFLICT OF INTEREST
https://doi.org/10.1039/c8cc04287j
12. Diez, A., Fornies, J., Larraz, C., Lalinde, E., Lopez, J.A.,
Martin, A., Moreno, M.T., and Sicilia, V., Inorg. Chem.,
2010, vol. 49, p. 3239.
No conflict of interest was declared by the authors.
SUPPLEMENTARY MATERIALS
https://doi.org/10.1021/ic902094c
Supplementary materials are available for this article at
https://doi.org/10.1134/S1070363220040143 and are accessible
for authorized users.
13. Forniés, J., Sicilia, V., Larraz, C., Camerano, J.A.,
Martín, A., Casas, J.M., and Tsipis, A.C., Organometallics,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 4 2020

SYNTHESIS OF CYCLOMETALATED PLATINUM(II) COMPLEX
653
2010, vol. 29, p. 1396.
26. Cavallo, G., Metrangolo, P., Pilati, T., Resnati, G., and
Terraneo, G., Cryst. Growth Des., 2014, vol. 14, p. 2697.
https://doi.org/10.1021/cg5001717
https://doi.org/10.1021/om901032v
14. Sicilia, V., Fuertes, S., Martín, A., and Palacios, A.,
Organometallics, 2013, vol. 32, p. 4092.
27. Kinzhalov, M.A., Kashina, M.V., Mikherdov, A.S.,
Katkova, S.A., and Suslonov, V.V., Russ. J. Gen. Chem.,
2018, vol. 88, p. 1180.
https://doi.org/10.1021/om400159g
15. Tritto, E., Chico, R., Ortega, J., Folcia, C.L., Etxebarria, J.,
Coco, S., and Espinet, P., J. Mater. Chem. (C), 2015,
vol. 3, p. 9385.
https://doi.org/10.1134/s107036321806021x
28. Kinzhalov, M.A., Zolotarev, A.A., and Boyarskiy, V.P.,
J. Struct. Chem., 2016, vol. 57, p. 822.
https://doi.org/10.1039/c5tc01802a
16. Wang, H., Bisoyi, H.K., Wang, L., Urbas, A.M.,
Bunning, T.J., and Li, Q., Angew. Chem. Int. Ed.,
2018, vol. 57, p. 1627.
https://doi.org/10.1134/s0022476616040302
29. Kinzhalov, M.A., Timofeeva, S.A., Luzyanin, K.V.,
Boyarskiy, V.P., Yakimanskiy, A.A., Haukka, M., and
Kukushkin, V.Y., Organometallics, 2016, vol. 35, p. 218.
https://doi.org/10.1021/acs.organomet.5b00936
30. Pawlak, T., Niedzielska, D., Vicha, J., Marek, R., and Paz-
derski, L., J. Organomet. Chem., 2014, vol. 759, p. 58.
https://doi.org/10.1016/j.jorganchem.2014.02.016
31. Pazderski, L., Pawlak, T., Sitkowski, J., Kozerski, L., and
Szlyk, E., Magn. Reson. Chem., 2009, vol. 47, p. 932.
https://doi.org/10.1002/mrc.2491
https://doi.org/10.1002/anie.201712781
17. Choi, S.J., Kuwabara, J., Nishimura, Y., Arai, T., and Kan-
bara, T., Chem. Lett., 2012, vol. 41, p. 65.
https://doi.org/10.1246/cl.2012.65
18. Boterashvili, M., Lahav, M., Shankar, S., Facchetti, A.,
and van der Boom, M.E., J. Am. Chem. Soc., 2014,
vol. 136, p. 11926.
https://doi.org/10.1021/ja5066587
19. Zhang, X., Li, B., Chen, Z.H., and Chen, Z.N.,
J. Mater. Chem., 2012, vol. 22, p. 11427.
32. Mikherdov, A.S., Tiuftiakov, N.Yu., Polukeev, V.A.,
and Boyarskii, V.P., Russ. J. Gen. Chem., 2018,
vol. 88, no. 4, p. 713.
https://doi.org/10.1039/c2jm30394a
20. Katkova, S.A., Mikherdov, A.S., Kinzhalov, M.A.,
Novikov, A.S., Zolotarev, A.A., Boyarskiy, V.P., and Ku-
kushkin, V.Yu., Chem. Eur. J., 2019, vol. 25, p. 8590.
https://doi.org/10.1002/chem.201901187
https://doi.org/10.1134/S1070363218040151
33. Mikherdov, A.S., Orekhova, Yu.A., and Boyarskii, V.P.,
Russ. J. Gen. Chem., 2018, vol. 88, no. 10, p. 2119.
https://doi.org/10.1134/S1070363218100158
34. Stephens, P.J., Devlin, F.J., Chabalowski, C.F., and
Frisch, M.J., J. Phys. Chem., 1994, vol. 98, vol. 11623.
https://doi.org/10.1021/j100096a001
21. Mikherdov, A.S., Kinzhalov, M.A., Novikov, A.S.,
Boyarskiy, V.P., Boyarskaya, I.A., Dar’in, D.V.,
Starova, G.L., and Kukushkin, V.Yu., J. Am. Chem. Soc.,
2016, vol. 138, p. 14129.
35. Sluch, I.M., Miranda, A.J., Elbjeirami, O.,
Omary, M.A., and Slaughter, L.M, Inorg. Chem., 2012,
vol. 51, p. 10728.
https://doi.org/10.1021/jacs.6b09133
22. Kinzhalov, M.A., Kashina, M.V., Mikherdov, A.S., Mozhe-
eva, E.A., Novikov, A.S., Smirnov, A.S., and Luzya-
nin, K.V., Angew. Chem. Int. Ed., 2018, vol. 57, p. 12785.
https://doi.org/10.1002/anie.201807642
https://doi.org/10.1021/ic301104a
36. McKinnon, J.J., Jayatilaka, D., and Spackman, M.A.,
Chem. Commun., 2007, p. 3814.
23. Ivanov, D.M., Kirina, Y.V., Novikov, A.S.,
Starova, G.L., and Kukushkin, V.Y., J. Mol. Struct.,
2016, vol. 1104, p. 19.
https://doi.org/10.1039/b704980c
37. Kinzhalov, M.A., Katkova, S.A., Doronina, E.P.,
Novikov, A.S., Eliseev, I.I., Ilichev, V.A., Kukinov, A.A.,
Starova, G.L., and Bokach, N.A., Z. Kristallogr. Cryst.
Mater., 2018, vol. 233, p. 795.
https://doi.org/10.1016/j.molstruc.2015.09.027
24. Bikbaeva, Z.M., Ivanov, D.M., Novikov, A.S., Ana-
nyev, I.V., Bokach, N.A., and Kukushkin, V.Yu., Inorg.
Chem., 2017, vol. 56, p. 13562.
https://doi.org/10.1515/zkri-2018-2075
38. Sicilia, V., Fornies, J., Casas, J.M., Martin, A., Lopez, J.A.,
Larraz, C., Borja, P., Ovejero, C., Tordera, D., and Bolink, H.,
Inorg. Chem., 2012, vol. 51, p. 3427.
https://doi.org/10.1021/acs.inorgchem.7b02224
25. Christopherson, J.C., Topic, F., Barrett, C.J., and Friscic, T.,
Cryst. Growth Des., 2018, vol. 19, p. 1245.
https://doi.org/10.1021/acs.cgd.7b01445
https://doi.org/10.1021/ic201910t
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 4 2020

654
KATKOVA et al.
39. Saegusa, T., Kobayash.S, Ito, Y., and Yasuda, N.,
J. Am. Chem. Soc., 1968, vol. 90, p. 4182.
https://doi.org/10.1021/ja01017a061
42. Sheldrick, G.M., Acta Crystallogr., 2008, vol. 64,
no. 1, p. 112.
https://doi.org/10.1107/S0108767307043930
43. Dolomanov, O.V., Bourhis, L.J., Gildea, R.J.,
Howard, J.A.K., and Puschmann, H., J. Appl. Crystallogr.,
2009, vol. 42, p. 339.
40. Chu, C., Ayres, J.A., Stefanescu, D.M., Walker, B.R.,
Gorman, C.B., and Parsons, G.N., J. Phys. Chem. C.,
2007, vol. 111, p. 8080.
https://doi.org/10.1107/S0021889808042726
44. CrysAlisPro, A.T., Version 1.171.36.20 (release 27-06-
2012).
https://doi.org/10.1021/jp065377r
41. Palatinus, L. and Chapuis, G., J. Appl. Crystallograllogr.,
2007, vol. 40, p. 786.
45. Bondi, A., J. Phys. Chem., 1964, vol. 68, p. 441.
https://doi.org/10.1021/j100881a503
https://doi.org/10.1107/s0021889807029238
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 4 2020