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Nikolaev Institute of Inorganic Chemistry
Siberian Branch of Russian Academy of Sciences
International workshop “CLUSPOM-Altay” 2016
on metal clusters and polyoxometallates
30 May – 3 June 2016
Book of abstracts
Altay, Katun village 2016
3
УДК 546
Book of abstracts of International workshop “CLUSPOM-Altay” 2016
Edited by dr. Ledneva A. Yu. NIIC SB RAS, 2016
ISBN 978-5-90168-838-0
This seminar is devoted to the meeting in the frame of joint French-Russian International
Laboratory LIA CLUSPOM (2015-2018) “Innovative Materials and Nanomaterials Based
on Tailor‐ Made Functional Building Blocks”.
Topics will encompass fundamental research on metal atom clusters and POM - synthesis
of new compounds, characterization of structures and properties, calculations, …- to the
integration of clusters and POM in applicative materials, nanomaterials and devices.
Building bridges between metal atom cluster chemistry and POM chemistry should enable
to create new fields of research to bring real breakthrough and innovations in molecular
synthesis, self-assembly processes, surface assembly and immobilization into composite
materials and integrated-molecular based systems for various applications. The long-term
scientific challenge is the design of innovative applicative inorganic hybrids based-
materials for different application fields like energy (storage and conversion), green
chemistry and processes, health (both curative and diagnostic), depollution, eco-conception,
low environmental impact chemicals, solar cells, biofuels, electronics, information
technology, nanotechnologies.
Scientists from Rennes, Versailles and Novosibirk will present new results and will discuss
future collaboration.
ISBN 978-5-90168-838-0 © Nikolaev Institute of Inorganic Chemistry
Siberian Branch of Russian Academy of Sciences, 2016
4
International workshop “CLUSPOM-Altay”
on metal clusters and polyoxometallates
30 May – 3 June 2016, Katun, Altay, Russia
30 May
10 -00 Departure to the place of seminar
18-00 Arrival to the workshop place
19-00 Welcome dinner
31 May
P.
9-30 S. Cordier LIA cluspom between France and Russia: past, present and future -
restirution of the CNRS-RFBR meeting held in Paris on April 29th
2016
10-30 M. Amela-Cortes Functional transition metal clusters as building blocks for
hybrid luminescent copolymers
11-00 M. Haouas Application of NMR to organic-polyoxometalate hybrids: from
solution chemistry to materials
11-30 M. Sokolov New polyoxometalate complexes of noble metals
12-00 C. Prestipino Structural aspects in oxygen reactivity in oxides
13-30 Lunch
14-30 A. Ivanov. Towards water-soluble high x-ray contrast octahedral rhenium
cluster complexes
15-00 M. Kozlova Low-dimensional vanadium tetrasulfide
15-30 M. Mikhailov Synthesis of a new molybdenum cluster iodide with butterfly
core: [Mo4OI12]2
16-00 Yu. Mironov Chemistry of Re12 cluster complexes
16-30 V. Muraveva Mixed-metal clusters based on {Re3Mo3Se8} core: preparation,
properties and dft calculations.
5
17-00 M. Ryzhikov Metal-metal bonding in hexanuclear mixted metal clusters of
molibdenum and rhenium
17-30 M. Shestopalov Hexanuclear rhenium cluster complexes and their prospects as
x-ray contrast agents
19-00 Dinner
1 June
8-00 Breakfast
Excursion to Chuiski tract
2 June
8-30 Breakfast
9-30 Y. Molard Clustomesogens: from the design to the device
10-00 A. Ledneva Molecular tectonics: hydrogen bonded networks based on metallic
clusters
10-30 R. Gautier
11-00 S. Flouquet
11-30 K. Costuas combined theoretical and time-resolved photoluminescence
investigations of [Mo6Bri8Br
a6]
2- metal cluster units: evidences of dual emission
12
12-00 E. Cadot
12-30 Yu. Vorotnikov Conjugates of luminescent cluster doped silica nanoparticles
with antibodies
13-00 Lunch
15-00 Poster session
16-00 Barbecue-party
3 June
8-30 Breakfast
10-00 Departure back to Novosibirsk
6
NOBLE METALS CONTAINING POLYOXONIOBATES
Pavel A. Abramov
Nikolaev Institute of Inorganic Chemistry SB RAS,
3 Akad. Lavrentiev Ave., Novosibirsk, 630090 Russia
The chemistry of polyoxometalates (POM) is a rapidly growing area of modern coordination
chemistry. One of the emerging research lines in this field is chemistry of polyoxoniobates and
tantalates, which offer various chemical challenges like generation of pentagonal building
blocks [1], nanosized catalysts for water splitting (WS) [2] etc. In this contribution we discuss the
use of [Nb6O19]8- and [Ta6O19]
8- as ligands for coordination of noble metals. This area has been
almost completely neglected prior to our work.
We have found that reaction of [(C6H6)RuCl2]2 and Na8[Ta6O19] gives, depending on the reagent
ratio, two new hybrid organometallic-POM complexes – Na10[{(C6H6)RuTa6O18}2(μ-O)]∙39.4H2O
(1:1 ratio) and Na4(trans-[{(C6H6)Ru}2Ta6O19]∙20H2O (2:1 ratio). In both cases the half-sandwich
fragments {(C6H6)Ru}2+ are coordinated as additional vertices to the {Ta3(μ2-O)3} triangles.
Reactions between [M6O19]8- (M = Nb, Ta) and [Cp*RhCl2]2 gives trans-[{Cp*Rh}2M6O19]
4-, that
was isolated and characterized with different methods as K4[{Cp*Rh}2Nb6O19]∙20H2O and
Cs4[{Cp*Rh}2Ta6O19]∙18H2O correspondingly. Grafting of {Cp*Ir}2+ fragments onto [M6O19]8- (M =
Nb, Ta) gives 1:1 and trans-1:2 complexes, which were fully characterized as sodium salts.
These reactions also can be transferred to the recently started by us water solution chemistry of
[(OH)TeNb5O18]6-. We isolated and characterized trans-[{Cp*M}2(OH)TeNb5O18]
2- (M = Rh, Ir). Te
atom locates in the central M4 plane that was found from x-ray and NMR.
In the present work complexation of platinum(IV) with [Nb6O19]8- was studied with different
techniques. Thus, a dimeric complex Cs2K10[Nb6O19{Pt(OH)2}]2∙13H2O when hexaniobate
[Nb6O19]8 reacts with Pt(IV) in 1:1 molar ratio, while increasing of the Pt/Nb6 ratio to 2:1 gives
crystals of a sandwich-type Cs2K10[(Nb6O19)2Pt]∙18H2O complex.
This work was supported by RScF 14-13-00645.
[1] Tsunashima, R.; Long, D.-L. Angew. Chem. Int. Ed. 2010, 49, 113.
[2] Huang, P.; Qin, C.; Su, Z.-M. J. Am. Chem. Soc., 2012, 134, 14004.
7
FUNCTIONAL TRANSITION METAL CLUSTERS AS BUILDING BLOCKS
FOR HYBRID LUMINESCENT COPOLYMERS
M. Amela-Cortes, S. Paofai, P. Lemoine, N. Dumait, S. Cordier, Y. Molard
Address: Institut des Sciences Chimiques de Rennes, Campus de Beaulieu, 35042, Rennes;
E-mail: [email protected]
Photoluminescent materials are playing a major role in applications related to photonics,
optoelectronics or lighting. Combining them with polymers allows the design of easy-to-shape-
functional materials with enhanced application versatility. The [(M6Li8)L
a6]
n- unit (a = apical, i =
inner, M = Mo, Re; L = halogen, chalcogen, 1< n <8)) constitutes the basic building block in the
octahedral cluster chemistry and is easily obtained via high temperature solid state synthesis.
Metallic clusters show unusual electronic, magnetic and optical properties due to the full
delocalisation of valence electrons on the whole metallic scaffold. In particular, they can be
highly emissive in the red-NIR area. However, their direct incorporation in high content into
polymer matrices is challenging because it requires a perfect balance between the interactions
of both components to avoid phase segregation. Over the years we have developped various
strategies in order to obtain highly luminescent homogeneous materials1-3. One of the most
promising is the use of electostatic interactions which allow the homogeneous incorporation of
inorganic clusters up to 50 %wt content3-5. In this work, the alkalin countercations of the
inorganic clusters are replaced by polymerizable surfactants which are specially design to afford
polymers for specific applications. In this presentation these different strategies and the
properties of the resulting hybrid polymers will be presented.
References: [1]. Y. Molard, et al. Chem. Eur. J., 2010, 16, 5613.
[2] Y. Molard, et al., Adv. Funct. Mater., 2013, 23, 4821.
[3]. M. Amela-Cortes, et al., J. Mater. Chem. C., 2014, 2, 1545.
[4] M. Amela-Cortes, et al., Dalton trans, 2016, 45, 237.
[5] M.Amela-Cortes et al. Chem. Commun.
8
LIA CLUSPOM BETWEEN FRANCE AND RUSSIA: PAST, PRESENT
AND FUTURE - RESTIRUTION OF THE CNRS-RFBR MEETING HELD IN
PARIS ON April 29th 2016
Stéphane Cordier
Institut des Sciences Chimiques de Rennes – Campus de Beaulieu – 35 042 Rennes Cedex
2016 is the fiftieth year of scientific and technologic collaboration between
France and Russia and the 20th anniversary of CNRS – RFBR cooperation.
To celebrate this 20th birthday, a meeting between officials of CNRS and
RFBR and in particular their respective presidents Alain FUCHS and
Vladislav PANCHENKO was held in Paris on April 29th 2016 followed by
presentations of major scientific collaborations between the two countries. At
this occasion, President Vladislav PANCHENKO brought his signature to the
LIA CLUSPOM as the last administrative brick for RFBR funding.
LIA CLUSPOM involves Institut des Sciences Chimiques de Rennes (ISCR), Institut Lavoiser de
Versailles (ILV) and Nikolaev Institute of Inorganic Chemistry from Novosibirsk (NIIC).
CLUSPOM is born from IDEMAT chemistry project in the frame of the Franco-Siberian Center of
Training and Research. It results in particular from collaborations begun at the beginning of 2000
and developed on one hand between ISCR and NIIC and on the other hand between ILV and
NIIC. It focuses on the development of a fundamental understanding that governs the chemical
formation pathways, the reactivity and the physical-chemistry properties of Cluster-and/or
Polyoxometalate-based materials. The scientific goals are based on further functionalization
strategies that expand the role of molecular chemistry in materials science applications such as
catalysis, energy conversion and storage, green chemistry and on integrating molecular-type
systems into composite materials and surfaces.
LIA CLUSPOM started in 2015 and will end in 2018. In this contribution, the goals of LIA, tasks
as well as workpackages will be reviewed and major results will be presented. It turns out that
LIA CLUSPOM was evaluated only on the French side and as such, it has been hitherto funded
by French tutelles of ISCR and ILV. Taking into account recommendations of Mr. Alexander
SHAROV and Prof. Alexander GABIBOV explained at the occasion of 20th anniversary of CNRS
– RFBR cooperation in Paris, all aspects of rules for RFBR funding and double CNRS-RFBR
evaluation for renewal of LIA will be exposed.
9
COMBINED THEORETICAL AND TIME-RESOLVED
PHOTOLUMINESCENCE INVESTIGATIONS OF [Mo6Bri8Bra
6]2- METAL
CLUSTER UNITS: EVIDENCES OF DUAL EMISSION
K. Costuas, A. Garreau, A. Bulou, B. Fontaine, J. Cuny, R. Gautier, M. Mortier, Y. Molard, J.-L.
Duvail, E. Faulques
Institut des sciences chimiques de Rennes, CNRS - Université de Rennes 1, Campus de
Beaulieu, F-35042 Rennes cedex, France
Developments of materials based on the assemblage of functional molecular building-blocks
necessitate a fine control and understanding of the physical properties of the molecular units,
both experimentally and theoretically. The luminescent [Mo6Bri8Bra
6]2- unit presents a large
absorption window from Ultra Violet (UV) to the visible (vis.) and a large emission window from
vis. to near Infra Red (NIR). These properties are exploited in materials such as luminescent
liquid crystals (LCD and lighting display applications) or multifunctional nanoparticles (bio-
labeling). Nevertheless, their photo-physical properties were not fully understood to date. Our
combined time-resolved photoluminescence (PL) and theoretical study reveals a dual
luminescence, and temperature and excitation wavelength dependency. By quantum chemical
studies, we show for the first time that important geometrical relaxations occur at the triplet
states by either the outstretching of an apex away from the square plane of the Mo6 octahedron
or by the elongation of one Mo-Mo bond. Our results demonstrate that the relaxation processes
before and after emission can be tracked via fast time-resolved spectroscopies. They also show
that the surrounding of the luminescent cluster unit and the excitation wavelength could be
modulated for target applications.1
Reference
[1] K. Costuas, A. Garreau, A. Bulou, B. Fontaine, J. Cuny, R. Gautier, M. Mortier, Y. Molard, J.-
L. Duvail, E. Faulques, S. Cordier, Phys. Chem. Chem. Phys., 2015, 17, 28574-28585
10
APPLICATION OF NMR TO ORGANIC-POLYOXOMETALATE HYBRIDS: FROM SOLUTION CHEMISTRY TO MATERIALS
Mohamed Haouas
Institut Lavoisier de Versailles, University of Versailles Saint Quentin en Yvelines (France)
Along with single crystal X-ray diffraction, nuclear magnetic resonance (NMR) spectroscopy is a
suitable tool for structural characterization of polyoxometalate (POM) compounds and both
techniques have contributed to the discovery of numerous novel structures during the last
decades. Several attractive active NMR nuclei, like ½ spins 183W, 31P, 29Si, etc., but also
quadrupolar nuclei like 95Mo, 27Al or 17O have been found to be useful probes for the state of
POMs in solution. NMR observables, i.e., chemical shifts, line-widths, relative signal intensities
and homonuclear and heteronuclear coupling constants provide the basis to identify the
structure and the interaction around the local environment of the observed nucleus. One of the
major advantages of NMR lies in the multiplicity and the flexibility of available experiments: from
one-dimensional (1-D) for various nuclei, to two-dimensional (2-D) experiments, in which one
can select the interactions to be separated and/or the nuclei to be correlated to each-other.
In this presentation, application of NMR to POMs chemistry is exemplified through some
representative recent studies either in solution or in solid state. Particular attention will be paid
on hybrid organic-POM systems based either on coordination chemistry or supramolecular
assembly, devoted for the development of new hierarchical systems potentially relevant for
many area of science such as catalysis, biology or electronics.
In an attempt to merge the chemistries of metal atom clusters and polyoxometalates via a
supramolecular host-guest approach, a third component namely cyclodextrin (CD) is introduced
to promote inclusion complexes integrating correlated structures and functions into well-defined
building blocks assemblies. Preliminary results showed that -CD leads to the spontaneous
formation of either molecular hybrid organic-inorganic complexes (Fig. 1) or infinite network
through long-range organization (Fig. 2) depending on the nature, the charge, the size, etc. of
the guest. The state of CD either in solution or solid state are monitored by NMR to probe local
the structure, the molecular organization and the interaction strength in these hybrid molecular
assemblies
Fig. 1: Top and side views of crystallographic structure of {[Ta6Br12(H2O)6]
2+}⊂[ -CD]2 Fig. 2: Hydrogel resulting from the supramolecular interactions in [P2W18O62]
6-/ -CD/[Ta6Br12(H2O)6]2+.
11
TOWARDS WATER-SOLUBLE HIGH X-RAY CONTRAST OCTAHEDRAL RHENIUM CLUSTER COMPLEXES
A.A. Ivanova,b, A.A. Krasilnikovaa, O.G. Kurskayaa, M.A. Gulyaevaa, A.Y. Alekseeva,
M.A. Shestopalova,b,c, Y.V. Mironovb,c, A.M. Shestopalova aScientific Institute of Experimental and Clinical Medicine, 2 Timakova st., 630060 Novosibirsk,
Russian Federation bNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev ave., 630090 Novosibirsk,
Russian Federation cNovosibirsk State University, 2 Pirogova st., 630090 Novosibirsk, Russian Federation
Nowadays a number of X-ray contrast agents based on 1,3,5-triiodobenzene and gadolinium are
used. However, the application of these compounds is often compromised by some
disadvantages, such as allergic and painful reactions as well as cardiovascular and kidney
disease. Thus, the development of more applicable radiocontrast agents is a very important
task. Octahedral rhenium cluster complexes [{Re6Q8}L6] (Q = S, Se, Te; L = organic or inorganic
ligand) can be considered as promising radiocontrast agents, since the recent studies revealed
that these cluster complexes showede high X-ray contrast (significantly higher than that of
currently used organic drugs) and relatively low toxicity, which, however is insufficient for
medical use. There are at least two ways to obtain less toxic compounds: the synthesis of new
cluster complexes with biocompatible ligands or the creation of a conjugate or adduct of the
cluster complexes with water soluble biocompatible organic polymers. In this work both these
approaches were demonstrated.
At first, we studied the cytotoxicity and intracellular localization in vitro of conjugates/adducts of
octahedral rhenium cluster complexes [{Re6Q8}L6]n– (Q = S, Se; L = SO3 (n = 10), OH (n = 4),
P(CH2CH2COO)3 (n = 16), CN (n = 4)) with polyethylene oxide Mv = 4000 (peg4) and 40000
(peg40) Da, dextran Mv = 70000 (dex70) Da and their oxidized forms (peg4.ox, peg40.ox,
dex70.4% and dex70.30%). Generally, it was found that a decrease of the toxicity took place.
Also, organic compounds based on isonicotinic acid were synthesized, and then they were
coordinated to the hexarhenium cores {Re6Q8}2+ through the ligand exchange reactions with
chalcohalide complexes Cs4[{Re6S8}X6] or Cs3[{Re6Se8}X6] (X = Cl, Br, I). Thus, organic
compounds N-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]pyridine-4-carboxamide (L1),
2,3,4,5,6-pentahydroxyhexyl pyridine-4-carboxylate (L2) and cluster complexes [{Re6Q8}(4-py-
COOH)4Br2], [{Re6Q8}(4-py-CONH2)4Br2], (Bu4N)2[{Re6Se8}(L1)2I4], [{Re6Q8}(L1)4Br2] (Q = S, Se)
were obtained. All synthesized compounds were characterized by X-ray single-crystal and
powder diffraction, IR- and NMR-spectroscopies, and elemental analysis.
This work was supported by the Russian Science Foundation (Grant 15-15-10006).
12
LOW-DIMENSIONAL VANADIUM TETRASULFIDE
Kozlova M.N.1, Fedorov V.E.1,2
1Nikolaev Institute of Inorganic Chemistry SB RAS,
Novosibirsk, Russia 2Novosibirsk State University
In the last few years preparation of nanosized low-dimensional metal chalcogenides attracted
wide attention due to their improved electronic, optical, catalytic properties etc. Although many of
the layered metal chalcogenides, such as MoS2, are well studied, some other chalcogenides
have received less attention by comparison. In particular, there has been an emerging interest in
vanadium tetrasulfide (VS4), which displays useful properties as a component of hybrids [1]. The
structure of VS4 can be regarded as quasi-one-dimensional with metal chains which are bonded
by weak van der Waals forces (interchain S…S distances >3.2 Å). We have synthesized VS4 by
a direct reaction between the elements. The bulk VS4 was investigated by a set of methods and
electrophysical properties of the pressed samples were studied. We further demonstrate that the
bulk may be ultrasonically dispersed in appropriate solvents to form colloids, similarly to the
layered chalcogenides. VS4 particles in colloids retain their phase identity and rod-shaped
morphology with lengths in the range of hundreds of nanometers. Isopropanol dispersion
exhibited the highest concentration (about 310 mgL-1) and stability (over 10 days) [2]. Thin films
of VS4 were prepared from isopropanol dispersions by two methods: filtration through membrane
filters with pore size 0.02 µm and spray-method. Decorating the surface with nanoparticles of
different types is an effective way to functionalize the material and bring new and enhanced
properties for many areas such as energy storage, catalysis and surface enhanced Raman
spectroscopy devices. Here we also report deposition of noble metal nanoparticles on the VS4
interface.
References
[1] C. S. Rout, B. H. Kim, X. Xu, J. Yang, H. Y. Jeong, D. Odkhuu, N. Park, J. Cho, H. S.
Shin, J. Am. Chem. Soc. 2013, 135, 8720 – 8725;
[2] M. N. Kozlova, Yu. V. Mironov, E. D. Grayfer, A. I. Smolentsev, V. I. Zaikovskii, N. A.
Nebogatikova, T. Yu. Podlipskaya, V. E. Fedorov. Chem. Eur. J. 2015, 21 (12), 4639–4645
Acknowledgements. This work was supported the Russian Science Foundation (project 14-13-
00674).
13
MOLECULAR TECTONICS: HYDROGEN BONDED NETWORKS
BASED ON METALLIC CLUSTERS
A.Yu. Ledneva,1 S. Ferlay,2 G. Daigre 3
1 Nikolaev Institute of Inorganic Chemistry, Novosibirsk, Russia
2 Laboratoire de tectonique Moléculaire du Solide, University of Strasbourg, Strasbourg, France
3 UMR “Institut des Sciences Chimiques de Rennes“, UR1-CNRS 6226, Université de Rennes 1,
Rennes, France
Molecular networks [1] in solid state have attracted considerable interest over the last years. The
molecular tectonics [2] approach is a viable strategy for the design of infinite periodic molecular
networks resulting from self-assembly processes between complementary tectons or building
blocks. Crystalline materials based on both organic and inorganic tectons are attractive because
they can exhibit a wide range of electronic, optical or magnetic properties that may be chemically
tuned by appropriate modifications of tectons.
The bis-amidinium-based tectons are interesting units for the generation of charge-assisted
hydrogen-bonded networks in the presence of anions behaving as hydrogen bond acceptors.
Combinations of such tectons with cyanometallates [M(CN)x]m- lead to formation 1D or 2D
networks with different architectures depending on
geometry, charge of the cyanometallates and the size of
dications [3].
Octahedral rhenium and molybdenum clusters
[M6Q8(CN)6]4– and (Q = S, Se, Br) are well known analogue
of octahedral [Fe(CN)6]4– [4].
The results of combination of bis-amidinium cations with clusters [Re6Q8(CN)6]4–/3- (Q = S, Se)
and [Mo6Br6Se2(CN)6]4– are reported herein.
References: 1. Metal-Organic Frameworks. Chem. Rev. 2012. 112(2): p. 673-1268. 2. Hosseini, M.W., Acc. Chem. Res., 2005. 38(4): p. 313-323. 3. Ferlay, S., et al., Crystengcomm, 2002. 4: p. 447-453. 4. Naumov, N.G., et al. J. Struct. Chem., 2000. 41(3): p. 499-520.
14
SYNTHESIS OF A NEW MOLYBDENUM CLUSTER IODIDE WITH
BUTTERFLY CORE: [Mo4OI12]2-
M. A. Mikhailov, P.A. Abramov, A. L. Gushchin, M. N. Sokolov
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences,
Prosp. Akad. Lavrentyeva 3, 630090 Novosibirsk, Russian Federation
e-mail address: [email protected]
Reaction of Mo(CO)6 with (C4H9)4NI and I2 in diglyme added a new butterfly cluster [Mo4OI12]2−,
an iodide analogue, to the family of [Mo4OX12]2− (X = Cl, Br) clusters [1]. The cluster was
crystallized as tetraphenylphosphonium salt as dark-brown crystals and characterized by X-ray
single-crystal diffraction, and tetrabutylammonium (TBA) salt was characterized by elemental
analyses, mass spectrometry, Energy-dispersive X-ray (EDX), IR, Raman and UV−vis
spectroscopies and CVA studies, molecular orbital calculations were carried out.
The anion has a butterfly array of molybdenum atoms with an internal dihedral angle of 117°.
There are six terminal iodine atoms in the anion, two
μ3-I and four μ2-I atoms. A μ4-oxygen atom nestled into
the Mo4 framework as shown in the figure. The
distances between hinge molybdenum atoms is
2.651(1) Å, which is slightly longer than 2.594(1) Å
found in the bromide analogue [1], whereas the
peripheral Mo-Mo distances are in the range 2.699(7)
÷ 2.733(3) Å. The µ4-O atom is at 2.074 (3) Å from the
wingtip Mo atoms and at 2.148 (3) Å from the hinge Mo
atoms, with respective Mo-O-Mo angles of 155.0(1)
and 76.2(1)°. The redox behavior of TBA2[Mo4OI12] in CH3CN was studied by CV in the presence of TBAPF6
(0.1M). The complex is irreversibly oxidized at Ea1 = 0.46 V, Ea
2 = 0.88 V (vs. Ag/AgCl) in the
range of 0 ÷ 1.3 V.
The solutions of TBA2[Mo4OI12] in CH3CN strongly absorb at 214 nm, 246 nm, 292 nm, 358 nm
with the relevant molar absorption coefficients ( , M–1cm–1) 6.93*107, 4.93*107, 3.44*107,
1.95*107 respectively.
The work has been done with the support of Russian Foundation For Basic Research, within the framework of a research project № 16-33-60016. References
[1] F. A. Cotton, X. Feng, M. Shang, S. Zhong. Inorg. Chem. 1993, 32, 1321-1326.
15
CHEMISTRY OF Re12 CLUSTER COMPLEXES
Yuri V. Mironova,b,c, Yakov M. Gayfulina, V.E. Fedorova
aNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev ave., 630090 Novosibirsk,
Russian Federation bScientific Institute of Clinical and Experimental Lymphology, 2 Timakova st., 630060
Novosibirsk, Russian Federation cNovosibirsk State University, 2 Pirogova st., 630090 Novosibirsk, Russian Federation
The unique twelve-nuclear cluster complex
[Re12CS17(CN)6]8– consists of two Re6 octahedra linked
by three μ-S-bridges and a μ6-carbon atom. The
dodecanuclear rhenium anionic complexes with terminal
hydroxo and Br– ligands [Re12CS17(OH)6]6– and
[Re12CS17Br6]6– were also obtained. Some properties of
these compounds were studied. Also we have found
that μ-S may be reversibly oxidized to μ-SO2. It was
recently shown that oxidation of μ-S ligands within the
bioctahedral [Re12CS14(μ-S)3(CN)6]6– cluster anion using
H2O2 led to formation of μ-SO2 and μ-SO3 products.
Now we found that [Re12CS14(μ-SO2)3(CN)6]6– cluster
anion can be reduced by chalcogenide anions in
aqueous media under mild conditions, yielding the
[Re12CS14(μ-S)3(CN)6]6– as the final product. All new
compounds were characterized by single-crystal X-ray
diffraction, elemental analyses and IR spectroscopy.
The presence of μ6-C was confirmed by 13C NMR and
by ESI mass spectrum.
This research was supported by the Russian Science Foundation (Grant No. 14-14-00192).
16
CLUSTOMESOGENS: FROM THE DESIGN TO THE DEVICE
Yann Molard,* Maria Amela-Cortes, Stephane Cordier
Institut des Sciences Chimiques de Rennes, Rennes, France
Liquid crystals (LC) have a big impact on our everyday life. They are most of the time associated to display technology,
[1] but can also be found in many other applications where electron, ion, or molecular
transporting are necessary, or in the fields of holography, spectroscopy, or biomedical.[2]
Thus, conferring new functionalities like luminescence to LC is a challenge of particular interest as photoluminescent materials play a key role in photonics, optoelectronics or lighting applications.
[3] In this frame, we develop
a new class of hybrid LC material called clustomesogen that contains red-NIR phosphorescent transition metal clusters.
[4] Before showing how their phosphorescence properties can be modulated, we will present
the three strategies used to design clustomesogens: i) a covalent approach in which organic LC promoters are covalently linked on an octahedral metallic cluster core,
[5] ii) a supramolecular one that
combines electrostatic and host guest interactions to associate the LC organic promoters with a Cs2Mo6Br14 ternary salt,
[6] and, iii) an ionic approach
[7] that takes advantage of the cluster units anionic
character to associate them with organic cations bearing mesogenic promoters.
Figure 1. Representation of clustomesogens obtained by the three approaches: a) covalent, b) ionic and c) supramolecular.
References [1] D.-K. Yang, S.-T. Wu, Fundamentals of liquid crystal devices, John Wiley & Sons, Ltd, 2006.
[2] J. W. Goodby, P. J. Collings, T. Kato, C. Tschierske, H. F. Gleeson, P. Raynes, Editors, Handbook of Liquid Crystals, Volume 8: Applications of Liquid Crystals, 2nd Edition, Wiley-VCH Verlag GmbH & Co. KGaA, 2014. [3] H. Coles, S. Morris, Nat. Photonics 2010, 4, 676. [4] a) F. A. Cotton, Inorg. Chem. 1964, 3, 1217. [5] a) Y. Molard, F. Dorson, V. Circu, T. Roisnel, F. Artzner, S. Cordier, Angew. Chem. Int. Ed. 2010, 49, 3351; b) M.
Amela-Cortes, F. Dorson, M. Prevot, A. Ghoufi, B. Fontaine, F. Goujon, R. Gautier, V. Circu, C. Meriadec, F. Artzner, H. Folliot, S. Cordier, Y. Molard, Chem. Eur. J. 2014, 20, 8561; c) V. Cîrcu, Y. Molard, M. Amela-Cortes, A. Bentaleb, P. Barois, V. Dorcet, S. Cordier, Angew. Chem. Int. Ed. 2015, 53, 10921 [6] a) S. K. Nayak, M. Amela-Cortes, C. Roiland, S. Cordier, Y. Molard, Chem. Commun. 2015, 51, 3774; b) S. K. Nayak, M. Amela-Cortes, M. M. Neidhardt, S. Beardsworth, J. Kirres, M. Mansueto, S. Cordier, S. Laschat, Y. Molard, Chem. Commun., 2016, 52, 3127 [7] a) Y. Molard, A. Ledneva, M. Amela-Cortes, V. Circu, N. G. Naumov, C. Meriadec, F. Artzner, S. Cordier, Chem. Mater. 2011, 23, 5122; b) M. Amela-Cortes, S. Cordier, N. G. Naumov, C. Meriadec, F. Artzner, Y. Molard, J. Mater. Chem. C 2014, 2, 9813; c) M. Prevot, M. Amela-Cortes, S. K. Manna, S. Cordier, T. Roisnel, H. Folliot, L. Dupont, Y. Molard, J. Mater. Chem. C 2015, 3, 5152; d) M. Prevot, M. Amela-Cortes, S. K. Manna, R. Lefort, S. Cordier, H. Folliot, L. Dupont, Y. Molard, Adv. Func. Mater. 2015, 25, 4966; e) S. M. Wood, M. Prévôt, M. Amela-Cortes, S. Cordier, S. J. Elston, Y. Molard, S. M. Morris, Adv. Optical Mater. 2015, 3, 10, 1368
17
MIXED-METAL CLUSTERS BASED ON {Re3Mo3Se8} CORE:
PREPARATION, PROPERTIES AND DFT CALCULATIONS.
V.K. Muraveva1, Y.M. Gayfulin1, D.A. Piryazev1,2, M.R. Ryzhikov1, I.N. Novozhilov1, S. Cordier3,
N.G. Naumov1,2 1 Nikolaev Institute of Inorganic Chemistry SB RAS. 3, Acad. Lavrentiev Ave., Novosibirsk,
630090, Russia 2 Novosibirsk State University, 2 Pirogova Str., Novosibirsk, 630090, Russia
3 Institut des Sciences Chimiques de Rennes, UMR 6226 UR1-CNRS, Universite´ de Rennes 1,
Campus de Beaulieu, 35042 Rennes Cedex, France
Chemistry of the octahedral chalcogenide clusters of a {M6Q8} (M = Re, Mo; Q = S, Se, Te) type
is in a stage of rapid development. An interest to these compounds is caused by a fascinate
chemistry and a set of perspective physical properties including structural features, redox
transformations of cluster core, magnetism and luminescence.
Recently, it was shown that nonisovalent partial substitution of metal atoms within the cluster
core significantly changes the electronic structure of the resulting compounds in comparison with
homometallic species [1,2]. Here we report a detailed experimental and theoretical study of
mixed-metal octahedral clusters with {Re3Mo3Se8}n core (n= –1 ÷ +2). We have found that
reaction between ReSe2, MoSe2 and KCN at the elevated temperatures leads to the formation of
polymeric compound having the composition K6[Re3Mo3Se8(CN)5]. The {Re3Mo3Se8}1– cluster
core has 24 cluster valence electrons (CVE) as confirmed by diamagnetism of compound.
Cluster excision reaction was realized in aqueous solution of KCN resulting in crystallization of
K5[Re3Mo3Se8(CN)6]∙10H2O cluster salt. In that compound, {Re3Mo3Se8}1+ core contains 22 CVE
indicating the two-electron oxidation during dissolution of cluster anion by air oxygen. Further
oxidation of cluster core becomes possible in the organic solvent. Metathesis reaction of
K5[Re3Mo3Se8(CN)6]∙10H2O and Ph4PCl resulted in the formation of paramagnetic compound
(Ph4P)4[Re3Mo3Se8(CN)6]∙CH3CN containing {Re3Mo3Se8}2+ core with 21 CVE.
Electronic structure and geometrical parameters of [Re3Mo3Se8(CN)6]n– anions were investigated
by a set of physical methods. A number of cluster salts were investigated by single-crystal XRD. 13C NMR study in aqueous solution confirmed the presence of two isomers in the ratio of 2:1.
Redox properties of the [Re3Mo3Se8(CN)6]n– cluster anion were investigated using cyclic
voltammetry in aqueous and CH3CN solutions. Spectroscopic investigations were strongly
supported by DFT calculations.
The present work is supported by the RFBR grant No 16-33-00085.
Authors are gratefully acknowledged to the LIA CLUSPOM between France and Russia.
References
[1] Y.M. Gayfulin, N et al. // Chem. Commun., 2013, 49, 10019-10021.
[2] S.B. Artemkina, et al. // Z. Anorg. Allg. Chem. 2010, 636, 483–491.
18
STRUCTURAL ASPECTS IN OXYGEN REACTIVITY IN OXIDES
C. Prestipino1, M. Bahout1, O. Hernandez1, S. Figueroa2, I. Moog3, A. Demourgues3 1Institut Sciences Chimiques de Rennes, UMR-CNRS 6226, France
2Institut de Chimie de la Matière Condensée de Bordeaux, UPR 9048, France
Laboratório Nacional de Luz Síncrotron (LNLS) CNPEM Campinas(SP), BRASIL
Oxide ion conduction is relevant topic in applied and fundamental material science due to the
importance of such phenomena for several different technological and industrial devices. The
most widely known applications are the catalysis as catalyst or catalyst promoter and the
construction of electrochemical cells used for energy conversion and/or energy storage.[1]
However despite decades of studies, the understanding at the atomic level often remains
severely limited such materials that are both structurally and chemically complex materials.
Effectively such complexity is a condicio sine qua non for oxide ion conduction that implies the
simultaneous presence of defects (vacancy or interstitial sites), and shallow potential energy
hypersurfaces between local arrangement[2].For such reason an accurate and in situ structural
characterization is a fundamental step in oxygen conductor characterization.
During the seminar two example of in situ characterization will be illustrated:
The fist example is an in-situ characterization of layered oxides for electrochemical application
with the use of neutron and synchrotron powder diffraction [3,4] while the second will describes
an X-Ray absorption spectroscopy characterization of a promising soot oxidation catalyst.[5]
Reference
[1] E.C. Subbarao, H.S. Maiti, Solid State Ion. 1984)11 p. 317–338. [2] N.L. Allan, et al., J. Mater. Chem. 2008, 18, p. 4124–4132.. [3] M. Bahout, et al., J. Mater. Chem. 2012, 22 p. 10560. [4] T. Broux, et al., Chem. Mater. 2013, 25, p. 4053–4063. [5] I. Moog, et al., J. Phys. Chem. C. 2014, 118, p. 22746–22753.
19
METAL-METAL BONDING IN HEXANUCLEAR MIXTED METAL
CLUSTERS OF MOLIBDENUM AND RHENIUM
Ryzhikov M.R.
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences,
3, Acad. Lavrentiev Ave., Novosibirsk, 630090, Russia
Novosibirsk State University, 2 Pirogova Str., Novosibirsk-90, 630090, Russia
The present work is devoted to the investigation of the metal-metal bonds in {Re6-xMoxS8(CN)6}
(x=0-6) clusters by the Electron Localization Function (ELF) topological method [1]. The
following clusters were calculated by VWN+BP86 density functional with TZ2P all electron basis
set: [Re6Mo0S8(CN6)]4-, [Re5Mo1S8(CN)6)
5-, [Re4Mo2S8(CN)6]6-
cis, [Re4Mo2S8(CN)6]6-
trans,
[Re3Mo3S8(CN)6]7-
fac, [Re3Mo3S8(CN)6]7-
mer, [Re2Mo4S8(CN)6]6-
cis, [Re2Mo4S8(CN)6]6-
trans,
[Re1Mo5S8(CN)6]5- and [Re0Mo6S8(CN)6]
6-.
From the analysis of the ELF basins population it is possible to make some assumptions about
metal-metal bonding in {Re6-xMoxS8(CN)6} (x=0-6) clusters. Valence V(Mo,Mo) ELF basins are
less populated than V(Re,Re) basins and the population of V(Mo,Re) basins lays somewhere
between them. The tendency to the formation of the less populated basin for Mo atom could
explain the 20 CSE electronic structure of [Re0Mo6S8(CN)6]6- cluster. In electron deficient
clusters like [Re1Mo5S8(CN)6]5- and [Re0Mo6S8(CN)6]
6- three-center MMM basins have almost
the same population as twocenter basins and lead to the additional stabilization of {M3}
fragments. In simplified form, the 20 CSE in [Re0Mo6S8(CN)6]6- could be presented as the set of
twelve 1e-2c bonds and eight 1e-3c bonds and the 24 CSE in [Re6Mo0S8(CN)6]6- could be
pictured as the set of twelve 2e-2c bonds. Interesting to note that the trisynaptic V(Re,Re,Mo)
basin were not found among the investigated clusters.
The work has been supported by RSF grant №16-12-10016. References
1. Silvi B., Savin A., Nature, 1994, 371, pp. 683-686.
20
HEXANUCLEAR RHENIUM CLUSTER COMPLEXES AND THEIR
PROSPECTS AS X-RAY CONTRAST AGENTS
M.A. Shestopalov,a,b* A.A. Ivanov,a A.O. Solovieva,b A.A. Krasilnikova,b
aNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev ave, 630090
Novosibirsk, Russian Federation bScientific Institute of Clinical and Experimental Lymphology, 2 Timakova st., 630060
Novosibirsk, Russian Federation
Radiocontrast agents are used in medicine to improve visibility of inner body structures in X-ray
imaging techniques. To date, the most of radiocontrast agents are based on 1,3,5-
triiodobenzene derivatives. Low toxicity and high solubility allowed these compounds to integrate
into a medical field. However, their application has some drawbacks like cardiovascular,
anaphylactic (allergic), painful effects, and probability of emergence contrast-induced
nephropathy. We believe that octahedral chalcogenide rhenium cluster complexes with the
general formula [{Re6Q8}L6]n (Q = S, Se or Te; L = apical organic or inorganic ligands) may
become alternative radiocontrast materials. In these compounds a cluster core {Re6Q8} may
potentially act as a radiocontrast component and the apical ligand environment similar to
substituent in 1,3,5-triiodobenzene radiocontrast agents may provide biocompatibility.
Thus, the aim of our research was to study radiopacity, cytotoxicity, intracellular localization in
vitro and acute intravenous toxicity in vivo of several octahedral rhenium cluster compounds with
different inner (Q) and outer (L) ligands, namely, Na4[{Re6Q8}(CN)6] and
Na2H8[{Re6Se8}(P(CH2CH2CONH2)(CH2CH2COO)2)6], to evaluate which cluster complex is more
promising for the application as X-ray contrast agent.
1) 2) 3)
4) 5) 6)
Figure Angiography of the mouse blood vessels with Na4[{Re6Te8}(CN)6]
This work was supported by the Russian Foundation for Basic Research (Grant 15-33-20083)
and by the Grant of President of the Russian Federation (MK 4054.2015.3).
21
NEW WAY TO MIXED NIOBIUM CONTAINING POLYOXOTUNGSTATES
Alexandra A. Shmakova, Pavel A. Abramov
NIkolaev Institute of Inorganic Chemistry SB RAS,
3 Akad. Lavrentiev Ave., Novosibirsk, 630090 Russia
Chemistry of polyoxometalates (POM) is a rapidly growing area of modern coordination
chemistry. Among numerous polyoxocomplexes Nb/W mixed-addendum POMs explored by
Klemperer, Hill, Finke et al., including Lindqvist-type [NbxW6–xO19](2+x)–, Keggin-type
[XW9Nb3O40]n– (n = 7, X = SiIV, GeIV; n = 6, X = PV, AsV), and Dawson-type
[P2W12(NbO2)6O56]12–, [P2W15Nb3O62]
9–, and [P2W17(NbO2)O61]7–, attracted attention because of
their unique characteristics. Such derivatives have good stability in acidic media owing to the
presence of the peroxide groups. Finally, inheriting the properties of polyoxoniobates, the Nb/W
mixed-addendum POMs also possess high nucleophilicity especially on Ot(Nb), after elimination
of the peroxide groups. Such complexes demonstrate photocatalytic activity toward water
oxidation process, can be used as precursors for Hydrodesulfurization Catalysts with
Isomerization Properties or can be active in the process for preparing linearly-extended
polyalkylenepolyamines. Traditional synthetic way to primary Nb/W mixed POMs is the reaction
of Nb-peroxo compounds prepared in situ by solubilizing of [Nb6O19]8– in H2O2 with lacunary
polyoxotungstates or sodium tungstate. This methodology was also used to produce unique
Ta/W complexes.
In this research we found a new efficient way to prepare a wide range of mixed Nb/W
complexes. Thinking along the way of using niobium peroxocomplexes gave us the new idea to
found new niobium precursor because of synthesis with H2O2 has the following disadvantages:
a) the excess of H2O2 destroys tungsten precursors and titration of peroxide with sodium sulfite
is needed that was demonstrated in details in the works by R.G. Finke et al.; b) to destroy the
niobium peroxocomplex prolonged heating is needed; c) the control of stoichiometry between Nb
and W is not simple because of a part of Nb can go to Nb2O5 during the addition. To avoid all of
these troubles we tried to found new niobium precursor and we found it.
This work was supported by RFBR (grant number 15-33-20651).
22
NEW POLYOXOMETALATE COMPLEXES OF NOBLE METALS
M.N. Sokolov, P.A. Abramov, and A.V. Anyushin
Nikolaev Institute of Inorganic Chemistry, Pr. Lavrentyeva 3, 630090,Novosibirsk, Russia
New hybrid POM based on Lindqvist-type hexametalates [M6O19]8- (M = Nb, Ta) and
organometallic fragments {Cp*Rh}2+ and {Cp*Ir}2+ have been isolated.
K4[(Cp*Rh)2Nb6O19]∙20H2O and Cs4[(Cp*Rh)2Ta6O19]∙18H2O were obtained from solutions with
{Cp*Rh}:[M6O19]8- stoichiometry 2:1. Reaction of the hexametalates with [Cp*IrCl2]2 in [M6O19]
8-
/{Cp*Ir}2+ 1:2 molar ratio gave A4[{Cp*Ir}2M6O19]∙xH2O (A = Na, M = Nb, x = 22; A = K, M = Nb, x
= 22; A = Na, M = Ta, x = 24). When [M6O19]8-/{Cp*Ir}2+ were reacted in 1:1 molar ratio, Nb and
Ta behave in a different way. For M = Nb, the product was an oxo-bridged dimer with linear Nb-
O-Nb central bridge, [{Cp*IrNb6O18}2( 2-O)]10-. For M = Ta only monomeric [{Cp*Ir}Ta6O19]6- was
detected. Solution behavior of new complexes was studied with NMR and ESI-MS techniques.
CV experiments demonstrate efficient electrocatalytic water oxidation catalyzed by
[{Cp*Ir}2Nb6O19]4-.
Reaction of siliconiobate K10[Nb2O2][SiNb12O40]∙16H2O with [(C6H6)RuCl2]2 gives
[{(C6H6)Ru}4SiNb12O40]8-, which contains Keggin-type [SiNb12O40]
16- with four coordinated
organometallic {(C6H6)Ru}2+ units. [VNb12O40]15- behaves similarly.
Reactivities of (Bu4N)4[PW11O39(OsVIN)] and (Bu4N)7[α2-P2W17O61(OsVIN)] have been
investigated. Cyclic voltammetry shows accessibility of the OsVII state upon oxidation of the
{OsN}3+ complexes. The nitride ligand can be removed with azide in CH3CN with the formation of
[PW11O39(OsIIICH3CN)]4- and [α2-P2W17O61(OsIIICH3CN)]7- thus making available POMs with
exchangeable ligand at the Os site. Related chemistry will be discussed.
This work was supported by Russian Scientific Foundation grant No. 14-13-00645
23
DIFFERENT LUMINESCENT MATERIALS BASED ON ORGANIC
POLYMERS AND MOLYBDENUM CLUSTER COMPLEXES N.A. Vorotnikova,a,b M.V. Edeleva,c K.A. Brylev,a,b,d Y.A. Vorotnikov,a,b
M.A. Shestopalova,b,d aNikolaev Institute of Inorganic Chemistry SB RAS, 3 Akad. Lavrentiev ave., 630090
Novosibirsk, Russia. b, Scientific Institute of Clinical and Experimental Lymphology, 2 Timakova st., 630060
Novosibirsk, Russia cNovosibirsk Institute of Organic Chemistry SB RAS, 9 Akad. Lavrentiev ave., 630090
Novosibirsk, Russia dNovosibirsk State University, 2 Pirogova st., 630090 Novosibirsk, Russian Federation
In this work octahedral halide molybdenum cluster complexes with the {Mo6X8}4+ core
were chosen as luminescent dyes due to their remarkable luminescence properties: long-lived
luminescence in the red region of the spectrum, high emission quantum yields and lifetimes.
Owing to these properties such complexes can find a number of biological and medical
applications. However, cluster complexes cannot be used in biology directly. They need to be
covered by or incorporated into matrix. At this work we took organic matrices.
Polystyrene with different functional groups (PS-SH, PS-COOH and PS-Py), which are
capable to form covalent bonds with cluster core, and halide cluster complexes
(Bu4N)2[{Mo6X8}(NO3)6] possessing good luminescence properties. The cluster complexes were
immobilized into the matrices by copolymerization. The effect of cluster complex amount on the
polymerization degree was studied. It was shown that such materials did not generate the
singlet oxygen. For each material luminescence properties were studied. The maximum
emission quantum yield was revealed for {Mo6I8}@PS-SH and it was constant in both the solid
state and water dispersion. Also the materials did not influence on Hep2 cells proliferation.
PMMA (poly(methyl methacrylate)) and PLA (polylactic acid) were chosen as next matrices. Also
the number of cluster complexes was expanded by compounds with high emission quantum
yields, in particular (Bu4N)2[{Mo6I8}(OOCCF3)6], (Bu4N)2[{Mo6I8}(OTs)6], etc. Particles with size of
70-200 nm were obtained. Through the research process we modified the cluster complexes to
increase their solubility in methyl methacrylate. Also, the luminescence properties of the
materials obtained were studied.
This work was supported by the Russian Science Foundation (Grant №14-14-00192).
24
CONJUGATES OF LUMINESCENT CLUSTER DOPED SILICA
NANOPARTICLES WITH ANTIBODIES
Y.A. Vorotnikov,a,b M.A. Shestopalov,a,b,c K.A. Brylev,a,b,c N.A. Vorotnikova,a,b
A.O. Solovieva,b Y.V. Mironova,c aNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev ave., 630090 Novosibirsk,
Russian Federation bScientific Institute of Clinical and Experimental Lymphology, 2 Timakova st., 630060
Novosibirsk, Russian Federation cNovosibirsk State University, 2 Pirogova st., 630090 Novosibirsk, Russian Federation
In this work we studied the process of the encapsulation of photoluminescent octahedral
molybdenum cluster complexes into a silica matrix. Namely, we developed photo- and
chemically stable luminescent silica nanoparticles (SNPs), capable of generating singlet oxygen.
The treatment of human epidermoid larynx carcinoma (Hep2) cell cultures with SNPs showed
that the particles rapidly entered into the cells in vitro and stayed in the cytoplasm for a long
time. They also had a high biocompatibility and a low cellular toxicity in darkness. However,
upon photoirradiation the internalised SNPs demonstrated significant photo-induced cellular
toxicity (Figure 1).
As antibodies for conjugation Herceptin
(Trastuzumab) and anti-Her2 antibody fragments
(miniantibody) were chosen. Both these antibodies
are capable to bind specifically with the HER2/neu
receptor, which is overexpressed by breast cancer
cells and become an important biomarker and target
of therapy breast cancer patients. The next step of
this research was to obtain their conjugates with
luminescent SNPs. To synthesize these conjugates
surface of SNPs was modified by epoxy groups, and
then the conjugates were obtained by the interaction
between epoxy groups of SNPs and amino groups of
antibodies. Thereupon for both these conjugates
cytotoxicity, cellular uptake and selectivity of
accumulation in SKBR3 cells (human breast
adenocarcinoma cells) with overexpression of
HER2/neu receptor in comparison with Hep2 cells with low expression of HER2/neu were
investigated. It was shown that the conjugates were selectively accumulated in cells with
overexpression of HER2/neu receptor.
This work was supported by the Russian Science Foundation (Grant №14-14-00192).
Figure 1. Viability of Hep2 cells treated by {Mo6I8}
0.01@SiO2 NPs after photoirradiation
(0.01 is a loading of (Bu4N)2[{Mo6I8}(NO3)6] in g per 1 g of final SiO2)
25
Научное издание
International workshop “CLUSPOM-Altay” 2016
on metal clusters and polyoxometallates
Book of abstracts
Ответственный за выпуск
К.х.н. ЛЕДНЕВА Александра Юрьевна
Техническое редактирование и верстка
Миронова Г.Н., Леднева А.Ю.
Федеральное государственное бюджетное учреждение науки
Институт неорганической химии им. А. В. Николаева
Сибирского отделения Российской академии наук
Просп. Акад. Лаврентьева, 3, Новосибирск 630090
