Publications by authors named "Maxim N Sokolov"

89 Publications

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties.

Molecules 2021 Sep 21;26(18). Epub 2021 Sep 21.

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, Russia.

A new monoiminoacenaphthenone 3,5-(CF)CH-mian (complex ) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl(dpp-mian)(CHCN)] () and [VOCl(3,5-(CF)CH-bian)(HO)][VOCl(3,5-(CF)CH-bian)]·2.85DME () from [VOCl(CHCN)(HO)] () or [VCl(THF)]. The structure of all compounds was determined using X-ray structural analysis. The vanadium atom in these structures has an octahedral coordination environment. Complex has an unexpected structure. Firstly, it contains 3,5-(CF)CH-bian instead of 3,5-(CF)CH-mian. Secondly, it has a binuclear structure, in contrast to , in which two oxovanadium parts are linked to each other through V=O···V interaction. This interaction is non-covalent in origin, according to DFT calculations. In structures and , non-covalent π-π staking interactions between acenaphthene moieties of the neighboring molecules (distances are 3.36-3.40 Å) with an estimated energy of 3 kcal/mol were also found. The redox properties of the obtained compounds were studied using cyclic voltammetry in solution. In all cases, the reduction processes initiated by the redox-active nature of the mian or bian ligand were identified. The paramagnetic nature of complexes and has been proven by EPR spectroscopy. Complexes and exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The yields of products of cyclohexane oxidation were 43% (complex ) and 27% (complex ). Based on the data regarding the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play the most crucial role in the reaction. The initial products in the reactions with alkanes are alkyl hydroperoxides, which are easily reduced to their corresponding alcohols by the action of triphenylphosphine (PPh). According to the DFT calculations, the difference in the catalytic activity of and is most likely associated with a different mechanism for the generation of OH radicals. For complex with electron-withdrawing CF substituents at the diimine ligand, an alternative mechanism, different from Fenton's and involving a redox-active ligand, is assumed.
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http://dx.doi.org/10.3390/molecules26185706DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8465707PMC
September 2021

Structure impact on photodynamic therapy and cellular contrasting functions of colloids constructed from dimeric Au(I) complex and hexamolybdenum clusters.

Mater Sci Eng C Mater Biol Appl 2021 Sep 31;128:112355. Epub 2021 Jul 31.

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov str., 420088 Kazan, Russian Federation.

Electrostatically driven self-assembly of [AuL] (L is cyclic PNNP ligand) with [{MoI}(L')] (L' = I, CHCOO) in aqueous solutions is introduced as facile route for combination of therapeutic and cellular contrasting functions within heterometallic colloids (Mo-Au). The nature of L' affects the size and aggregation behavior of crystalline Mo-Au aggregates, which in turn affect the luminescence of the cluster units incorporated into Mo-Au colloids. The spin trap facilitated electron spin resonance spectroscopy technique indicates that the level of ROS generated by Mo-Au colloids is also affected by their size. Both (L' = I, CHCOO) Mo-Au colloids undergo cell internalization, which is enhanced by their assembly with poly-DL-lysine (PL) for L' = CHCOO, but remains unchanged for L' = I. The colloids PL-Mo-Au (L' = CHCOO) are visualized as huge crystalline aggregates both outside and inside the cell cytoplasm by confocal microscopy imaging of the incubated cells, while the smaller sized (30-50 nm) PL-Mo-Au (L' = I) efficiently stain the cell nuclei. Quantitative colocalization analysis of PL-Mo-Au (L' = CHCOO) in lysosomal compartments points to the fast endo-lysosomal escape of the colloids followed by their intracellular aggregation. The cytotoxicity of PL-Mo-Au differs from that of Mo and Au blocks, predominantly acting through apoptotic pathway. The photodynamic therapeutic effect of the PL-Mo-Au colloids on the cancer cells correlates with their intracellular trafficking and aggregation.
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http://dx.doi.org/10.1016/j.msec.2021.112355DOI Listing
September 2021

Zn(II) Heteroleptic Halide Complexes with 2-Halopyridines: Features of Halogen Bonding in Solid State.

Molecules 2021 Jun 3;26(11). Epub 2021 Jun 3.

Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva St. 3, 630090 Novosibirsk, Russia.

Reactions between Zn(II) dihalides and 2-halogen-substituted pyridines 2-XPy result in a series of heteroleptic molecular complexes [(2-XPy)ZnY] (Y = Cl, X = Cl (), Br (), I (); Y = Br, X = Cl (), Br (), I (), Y = I, X = Cl (), Br (), and I ()). Moreover, - are isostructural (triclinic), while and are monoclinic. In all cases, halogen bonding plays an important role in formation of crystal packing. Moreover, - demonstrate luminescence in asolid state; for the best emitting complexes, quantum yield (QY) exceeds 21%.
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http://dx.doi.org/10.3390/molecules26113393DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8199927PMC
June 2021

Coordination capacity of Keggin anions as polytopic ligands: case study of [VNbO].

Dalton Trans 2021 May;50(20):7078-7084

Nikolaev Institute of Inorganic Chemistry, 3 Akad. Lavrentiev Ave., 630090, Russia.

Reaction of Na9H4[VNb12O40{NbO(CO3)}2] with [(C6H6)RuCl2]2 (molar ratio {VNb12} : {(C6H6)Ru} = 1 : 4) in aqueous solution gives a mixture of [α-{(C6H6)Ru}4VNb12O40]7- and [α-{(C6H6)Ru}3VNb12O40]9-. Direct acetone diffusion into mother liquor leads to crystallization of Na6H[α-{(C6H6)Ru}4VNb12O40]·41.25H2O (1), characterized by single crystal X-ray diffraction (SCXRD). This anion has four organometallic fragments coordinated to the α-Keggin type [VNb12O40]15- backbone in different manner. Three {(C6H6)Ru}2+ groups cap triangular faces and one group a rectangular face of [VNb12O40]15-. Equilibrated mixture of [α-{(C6H6)Ru}4VNb12O40]7- and [α-{(C6H6)Ru}3VNb12O40]9- was studied by 1H DOSY NMR, HPLC-ICP-AES and HPLC-ESI-MS combined techniques. Direct chromatographic separation of these complexes results in unexpected transformation of both species into [α-{(C6H6)Ru}5VNb12O40]5-, isolated and characterized as Na5[α-{(C6H6)Ru}5VNb12O40]·16H2O (2). This anion contains five coordinated organometallic groups occupying both triangular and rectangular faces.
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http://dx.doi.org/10.1039/d1dt00765cDOI Listing
May 2021

Keggin-type polyoxometalate 1 : 1 complexes of Pb(II) and Bi(III): experimental, theoretical and luminescence studies.

Dalton Trans 2021 May;50(20):6913-6922

Nikolaev Institute of Inorganic Chemistry, 3 Akad. Lavrentiev Ave. 630090, Russia.

Bi3+ and Pb2+ uptake by a monolacunary Keggin-type [PW11O39]7- anion leads to the formation of [PW11O39Bi]4- and [PW11O39Pb]5- complexes with a stereochemically active lone pair at the incorporated heterometal. The two complexes were isolated as (TBA)4[PW11O39Bi] (1) and (TBA)5[PW11O39Pb] (2) and characterized by 31P and 183W NMR spectroscopy, high-resolution electrospray mass-spectrometry (HR-ESI-MS) and cyclic voltammetry (CV). EXAFS and XANES data confirm the unchanged oxidation state and ψ-square pyramidal geometry of Bi3+ and Pb2+ in 1 and 2. DFT calculations were used in order to (i) confirm the absence of ligands attached to the heterometal sites in both complexes and localize the lone pair, and (ii) assign all signals in the 183W NMR spectra. Complexes 1 and 2 demonstrate photoluminescence (PL). A reversible change in the PL spectra of both complexes in the presence of water vapor has been detected. On the contrary, PL data for sandwich-type ((CH3)4N)4K3[H4(PW11O39)2Bi]·25H2O (3) do not show sensitivity to water vapor.
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http://dx.doi.org/10.1039/d1dt00499aDOI Listing
May 2021

Oxochloroselenate(IV) with Incorporated {Cl }: The Case of Strong Cl⋅⋅⋅Cl Halogen Bonding.

Chemistry 2021 Jun 21;27(36):9292-9294. Epub 2021 May 21.

Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva St. 3, 630090, Novosibirsk, Russia.

Reaction of SeO , tetramethylammonium (TMA) chloride, aqueous HCl and Cl yields oxochloroselenate with incorporated Cl units, TMA {[Se O Cl ](Cl )}. The main feature of this compound is the strong (up to 3.5 kcal mol , according to DFT calculations) Cl⋅⋅⋅Cl bonding, which is also detected by Raman spectroscopy.
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http://dx.doi.org/10.1002/chem.202101024DOI Listing
June 2021

Paramagnetic Rhenium Iodide Cluster with N-Heterocyclic Carbene.

Inorg Chem 2021 May 20;60(9):6746-6752. Epub 2021 Apr 20.

Nikolaev Institute of Inorganic Chemistry SB RAS, Prosp. Lavrentieva 3, 630090 Novosibirsk, Russia.

-Trirhenium nonaiodide ReI reacts with 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) to produce the novel 13-electron paramagnetic cluster ReI(IMes), which was characterized by means of X-ray diffraction analysis, ESR spectroscopy, magnetometry, and quantum chemistry.
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http://dx.doi.org/10.1021/acs.inorgchem.1c00568DOI Listing
May 2021

"Host in Host" Supramolecular Core-Shell Type Systems Based on Giant Ring-Shaped Polyoxometalates.

Angew Chem Int Ed Engl 2021 Jun 31;60(25):14146-14153. Epub 2021 Mar 31.

Institut Lavoisier de Versailles, CNRS, UVSQ, Université Paris-Saclay, Versailles, France.

Herein, we show how the chaotropic effect arising from reduced molybdate ions in acidified aqueous solution is able to amplify drastically weak supramolecular interactions. Time-resolved Small Angle X-ray Scattering (SAXS) analysis suggests that molybdenum-blue oligomeric species form huge aggregates in the presence of γ-cyclodextrin (γ-CD) which results in the fast formation of nanoscopic {Mo }-based host-guest species, while X-ray diffraction analysis reveals that the ending-point of the scenario results in an unprecedented three-component well-ordered core-shell-like motif. A similar arrangement was found by using preformed hexarhenium chalcogenide-type cluster [Re Te (CN) ] as exogenous guest. This seminal work brings better understanding of the self-assembly processes in general and gives new opportunities for practical applications in the design of complex multicomponent materials via the simplicity of the non-covalent chemistry.
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http://dx.doi.org/10.1002/anie.202102507DOI Listing
June 2021

Rule, Not Exclusion: Formation of Dichlorine-Containing Supramolecular Complexes with Chlorometalates(IV).

Inorg Chem 2021 Mar 24;60(6):4171-4177. Epub 2021 Feb 24.

Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Lavrentieva St., Novosibirsk, Russia.

Supramolecular derivatives of chlorostannate(IV) and -plumbate(IV) with {Cl} units, Cat{[MCl](Cl)} (-; M = Sn, Pb, cat = 1-methylpyridinium (1-MePy), tetramethylammonium (TMA)) were prepared and characterized by X-ray diffractometry and Raman spectroscopy. In particular, the TMA-containing complexes demonstrate remarkable thermal stability, releasing Cl only at elevated temperatures.
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http://dx.doi.org/10.1021/acs.inorgchem.1c00436DOI Listing
March 2021

Unexpected Polymorphism in Bromoantimonate(III) Complexes and Its Effect on Optical Properties.

Inorg Chem 2021 Feb 26;60(4):2797-2804. Epub 2021 Jan 26.

Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva St., 630090 Novosibirsk, Russia.

Reactions of [SbBr] containing HBr solutions with bromide salts of 1,1'-(1,2-ethanediyl)bis(pyridine) (PyC) or 1,1'-(1,2-ethanediyl)bis(3,5-dimethylpyridine) (3,5-MePyC) initially result in the formation of the deep orange complexes Cat[SbBr] ( and ), featuring unusual Sb···Br interactions in the solid state. In the mother liquor, transforms into discrete binuclear (CPy)[SbBr], which demonstrates polymorphism (triclinic and monoclinic ), while transforms into polymeric (3,5-MePy){[SbBr]} (). DFT calculations reveal that the system of noncovalent Sb···Br contacts may be responsible for the appearance of the observed optical properties (unusual deep orange coloring).
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http://dx.doi.org/10.1021/acs.inorgchem.0c03699DOI Listing
February 2021

Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {MoPdS}.

Molecules 2021 Jan 21;26(3). Epub 2021 Jan 21.

FRC Kazan Scientific Center of RAS, Arbuzov Institute of Organic and Physical Chemistry, Arbuzov Str. 8, 420088 Kazan, Russia.

Reaction of heterometallic cubane-type cluster complexes-[Mo{Pd(dba)}SCl(dbbpy)]PF, [Mo{Pd(tu)}SCl(dbbpy)]Cl and [Mo{Pd(dba)}S(acac)(py)]PF, where dba-dibenzylideneacetone, dbbpy-4,4'-di--butyl-2,2'-bipyridine, tu-thiourea, acac-acetylacetonate, py-pyridine, with white phosphorus (P) in the presence of water leads to the formation of phosphorous acid HPO as the major product. The crucial role of the Pd atom in the cluster core {MoPdS} has been established in the hydrolytic activation of P molecule. The main intermediate of the process, the cluster complex [Mo{PdP(OH)}SCl(dbbpy)] with coordinated P(OH) molecule and phosphine PH, have been detected by P NMR spectroscopy in the reaction mixture.
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http://dx.doi.org/10.3390/molecules26030538DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7864515PMC
January 2021

Photodynamic Inactivation of Biofilms Using a Hexanuclear Molybdenum Complex Embedded in Transparent polyHEMA Hydrogels.

ACS Biomater Sci Eng 2020 12 19;6(12):6995-7003. Epub 2020 Nov 19.

Departamento de Química Inórganica y Orgánica, Universitat Jaume I, Av. Sos Baynat s/n, 12071 Castellón, Spain.

Three new photoactive polymeric materials embedding a hexanuclear molybdenum cluster (BuN)[MoI(CHCOO)] () have been synthesized and characterized by means of Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and emission spectroscopy. The materials are obtained in the format of transparent and thin sheets, and the formulations used to synthesize them are comprised of 2-hydroxyethyl methacrylate (HEMA), as a polymerizable monomer, and ethylene glycol dimethacrylate (EGDMA) or poly(ethylene glycol)dimethacrylate (PEGDMA), as cross-linkers. All the polymeric hydrogels generate singlet oxygen (O) upon irradiation with visible light (400-700 nm), as demonstrated by the reactivity toward two chemical traps of this reactive species (9,10-dimethylanthracene and 1,5-dihydroxynaphthalene). Some differences have been detected between the photoactive materials, probably attributable to variations in the permeability to solvent and oxygen. Notably, one of the materials resisted up to 10 cycles of photocatalytic oxygenation reactions of 1,5-dihydroxynaphthalene. All three of the polyHEMA hydrogels doped with are efficient against biofilms when irradiated with blue light (460 nm). The material made with the composition of 90% HEMA and 10% PEGDMA () is especially easy to handle, because of its flexibility, and it achieves a notable level of bacterial population reduction (3.0 log CFU/cm). The embedding of in cross-linked polyHEMA sheets affords a protective environment to the photosensitizer against aqueous degradation while preserving the photochemical and photobactericidal activity.
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http://dx.doi.org/10.1021/acsbiomaterials.0c00992DOI Listing
December 2020

One-Dimensional Diiodine-Iodobismuthate(III) Hybrids Cat{[BiI](I)}: Syntheses, Stability, and Optical Properties.

Inorg Chem 2020 Dec 17;59(23):17320-17325. Epub 2020 Nov 17.

Nikolaev Institute of Inorganic Chemistry (NIIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Lavrentieva Street, Novosibirsk 630090, Russia.

One-dimensional iodine-rich iodobismuthates(III), Cat{[BiI](I)} [Cat = 1,4-MePy () and 1-EtBMAP ()], feature the highest amount of "trapped" diiodine units in polyhalogen-halometalates of p-block elements. Both complexes have narrow optical band gaps (1.55 and 1.63 eV, respectively) and moderate thermal stability.
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http://dx.doi.org/10.1021/acs.inorgchem.0c02599DOI Listing
December 2020

Proton motion inside [(DMF)H][WCl]: structural, Raman and luminescence studies.

Phys Chem Chem Phys 2020 Nov 3;22(43):25344-25352. Epub 2020 Nov 3.

Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Akad. Lavrentiev Ave, 630090 Novosibirsk, Russia.

Protonation of DMF by (HO)[WCl] results in the appearance of strongly proton coupled [(DMF)H] dimers. Such units are captured as the cationic part of [(DMF)H][WCl] (1). The proton behavior in such dimers was studied for the first time with single crystal X-ray diffraction (XRD) and H MAS NMR, Raman and photoluminescence (PL) spectroscopic techniques. The experimental data reveal the presence of two types of [(DMF)H] dimers in 1 (cisoidal and transoidal, with respect to the mutual orientations of their C-O groups) which differ in terms of the degree to which they interact with the cluster anions as the temperature decreases. At room temperature all the OO distances in the [(DMF)H] dimers are very short (2.375 Å) and almost equal. H MAS NMR spectra show a resonance line at 18.7 ppm which is very close to that observed in sodium hydrogen maleate with a strong hydrogen bond belonging to a single-well potential of proton motion. The temperature decrease leads to the differentiation of [(DMF)H] dimers due to the elongation of the OO distance in one pair while keeping a practically constant OO distance in the second pair. The analysis of the cation-anion interactions reveals a strong difference between these two types of dimers which results from the shifting of one DMF molecule toward a terminal Cl ligand of the cluster anion. The DFT calculations were used to show the difference in OHO stretches for two different dimers. Moreover, we have found the PL of such dimeric units in the solid state. The temperature screening of the PL behavior demonstrates two types of luminescent centers at low temperatures which coalesce at 298 K. The proton motion in the hydrogen bond was studied using Raman spectroscopy, which was beneficial to monitor the complex behavior over a very broad temperature range from 5 to 298 K. According to the Raman data, we are dealing with a symmetric double-well potential for the hydrogen bond at room temperature, which becomes a broad single well potential below 110 K for the [(DMF)H] cation with a longer OO distance (the cisoidal isomer) and below 60 K for the [(DMF)H] cation with a shorter OO distance (the transoidal isomer).
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http://dx.doi.org/10.1039/d0cp04152aDOI Listing
November 2020

Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns.

Molecules 2020 Sep 23;25(19). Epub 2020 Sep 23.

G.A. Razuvaev Institute of Organometallic Chemistry RAS, 603950 Nizhny Novgorod, Russia.

Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth-elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived from aminohydroxamic acid, in order to compare the coordination ability of Bi with the similarly sized La ions. A polynuclear tyrosinehydroximate Bi(OH)[15-MC-5](NO) () was obtained according to the synthetic routes previously described for water-soluble Ln(III)-Cu(II) 15-MC-5 metallacrowns. Correlations between structural parameters of Bi(III) and Ln(III) complexes were analyzed. DFT calculations confirmed the similarity between molecular structures of the model bismuth(III) and lanthanum(III) tyrosinehydroximate 15-metallacrowns-5. Analysis of the electronic structures revealed, however, stronger donor-acceptor interactions between the central ion and the metallamacrocycle in the case of the lanthanum analogue. Thermochromic properties of were studied.
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http://dx.doi.org/10.3390/molecules25194379DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7582670PMC
September 2020

A Sterically Hindered Derivative of 2,1,3-Benzotelluradiazole: A Way to the First Structurally Characterised Monomeric Tellurium-Nitrogen Radical Anion.

Chemistry 2020 Nov 8;26(64):14688-14699. Epub 2020 Oct 8.

Novosibirsk State University, Pirogova St. 2, 630090, Novosibirsk, Russia.

Interaction of the tetradentate redox-active 6,6'-[1,2-phenylenebis(azanediyl)]bis(2,4-di-tert-butylphenol) (H L) with TeCl leads to neutral diamagnetic compound TeL (1) in high yield. The molecule of 1 has a nearly planar TeN O fragment, which suggests the formulation of 1 as Te L , in agreement with the results of DFT calculations and QTAIM and NBO analyses. Reduction of 1 with one equivalent of [CoCp ] leads to quantitative formation of the paramagnetic salt [CoCp ] [1] , which was characterised by single-crystal XRD. The solution EPR spectrum of [CoCp ] [1] at room temperature features a quintet due to splitting on two equivalent N nuclei. Below 150 K it turns into a broad singlet line with two weak satellites due to the splitting on the Te nucleus. Two-component relativistic DFT calculations perfectly reproduce the a( N) HFI constants and A ( Te) value responsible for the low-temperature satellite splitting. Calculations predict that the additional electron in 1 is localised mainly on L, while the spin density is delocalised over the whole molecule with significant localisation on the Te atom (≥30 %). All these data suggest that 1 can be regarded as the first example of a structurally characterised monomeric tellurium-nitrogen radical anion.
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http://dx.doi.org/10.1002/chem.202002799DOI Listing
November 2020

Cyclodextrin-Assisted Hierarchical Aggregation of Dawson-type Polyoxometalate in the Presence of {ReSe} Based Clusters.

Inorg Chem 2020 Aug 24;59(16):11396-11406. Epub 2020 Jul 24.

Institut Lavoisier de Versailles, UMR 8180 CNRS, UVSQ, Université Paris-Saclay, Versailles, France.

The association of metallic clusters (CLUS) and polyoxometalates (POM) into hierarchical architectures is achieved using γ-cyclodextrin (γ-CD) as a supramolecular connector. The new self-assembled systems, so-called CLUSPOM, are formed from Dawson-type polyoxometalate [PWO] and electron-rich rhenium clusters. It is worth noting that a cluster-based cation [{ReSe}(HO)] on one hand and a cluster-based anion on the other hand [{ReSe}(CN)] can be associated with the anionic POM. In the absence of the supramolecular connector, a "CLUSPOM salt" was obtained from aqueous solution of the cationic cluster and the polyoxometalate. In this solid, the arrangement between the polymetallic building blocks is mainly governed by long-range Coulombic interactions. In the presence of γ-CD, the Dawson anion and the cationic cluster are assembled differently, forming a hierarchical supramolecular solid, K[{ReSe}(HO)]{[PWO]@2γ-CD}·42HO, where the organic macrocycle acts as a ditopic linker between the inorganic building blocks. In such an edifice, the short-range molecular recognition dominates the long-range Coulombic interactions leading to a specific three-dimensional organization. Interestingly, the assembling of anionic POM [PWO] with the anionic rhenium cluster [{ReSe}(CN)] is also achieved with γ-CD despite the repulsive forces between the nanosized anions. The resulting solid, K{[{ReSe}(CN)]@2γ-CD}[PWO]·33HO, is built from 1:2 inclusion complexes {[{ReSe}(CN)]@2γ-CD} linked by a POM unit interacting with the exterior wall of the organic macrocycle. Multinuclear NMR and small-angle X-ray scattering investigations support supramolecular preorganization in aqueous solution prior to crystallization.
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http://dx.doi.org/10.1021/acs.inorgchem.0c01160DOI Listing
August 2020

Memory devices based on novel alkyl viologen halobismuthate(iii) complexes.

Chem Commun (Camb) 2020 Aug;56(64):9162-9165

Institute for Problems of Chemical Physics RAS, Semenov Prospect 1, Chernogolovka, 142432, Russia and Skolkovo Institute of Science and Technology, Nobel St. 3, Moscow, 143026, Russia.

Four novel halobismuthate(iii) complexes with alkyl viologen cations: (R2Viol)2[Bi2X10] (R = n-butyl, n-pentyl, X = Cl, Br) have been synthesized. Both chloride complexes revealed photochromic behavior and were successfully utilized for the fabrication of OFET-based memory devices with high switching coefficients and good write-read-erase cycling stability.
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http://dx.doi.org/10.1039/d0cc03732jDOI Listing
August 2020

Enhanced Photocatalytic Activity and Stability in Hydrogen Evolution of Mo Iodide Clusters Supported on Graphene Oxide.

Nanomaterials (Basel) 2020 Jun 28;10(7). Epub 2020 Jun 28.

Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Avenida de los Naranjos s/n, 46022 Valencia, Spain.

Catalytic properties of the cluster compound (TBA)[MoI(OCCH)] (TBA = tetrabutylammonium) and a new hybrid material (TBA)[email protected] (GO = graphene oxide) in water photoreduction into molecular hydrogen were investigated. New hybrid material (TBA)[email protected] was prepared by coordinative immobilization of the (TBA)[MoI(OCCH)] onto GO sheets and characterized by spectroscopic, analytical, and morphological techniques. Liquid and, for the first time, gas phase conditions were chosen for catalytic experiments under UV-Vis irradiation. In liquid water, optimal H production yields were obtained after using (TBA)[MoI(OCCH)] and (TBA)[email protected]) catalysts after 5 h of irradiation of liquid water. Despite these remarkable catalytic performances, "liquid-phase" catalytic systems have serious drawbacks: the cluster anion evolves to less active cluster species with partial hydrolytic decomposition, and the nanocomposite completely decays in the process. Vapor water photoreduction showed lower catalytic performance but offers more advantages in terms of cluster stability, even after longer radiation exposure times and recyclability of both catalysts. The turnover frequency (TOF) of (TBA)[email protected] is three times higher than that of the microcrystalline (TBA)[MoI(OCCH)], in agreement with the better accessibility of catalytic cluster sites for water molecules in the gas phase. This bodes well for the possibility of creating {MoI}-based materials as catalysts in hydrogen production technology from water vapor.
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http://dx.doi.org/10.3390/nano10071259DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7407389PMC
June 2020

Opening the Third Century of Polyhalide Chemistry: Thermally Stable Complex with "Trapped" Dichlorine.

Chemistry 2020 Nov 1;26(61):13776-13778. Epub 2020 Oct 1.

Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva St. 3, 630090, Novosibirsk, Russia.

Unlike polyhalides of heavier halogens, polychlorides still remain exotic curiosities. Herein, we report preparation and investigation of complexes Cat {[TeCl ](Cl )} (cat=1-methylpyridinium (1) and tetramethylammonium (2)) where dichlorine units are "trapped" by chlorotellurate(IV) anions via a system of non-covalent Cl⋅⋅⋅Cl interactions. Complex 2 reveals a record thermal stability (>100 °C) for inclusion compounds with Cl , indications that such compounds can be used as solid Cl source.
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http://dx.doi.org/10.1002/chem.202002014DOI Listing
November 2020

From Specific γ-CD/[Nb Cl (H O) ] Recognition to Biological Activity Tuning.

Chemistry 2020 Jun 19;26(33):7479-7485. Epub 2020 May 19.

Nikolaev Institute of Inorganic Chemistry SB RAS, 3 acad. Lavrentiev ave., 630090, Novosibirsk, Russia.

Specific molecular recognition of γ-cyclodextrin (γ-CD) by the cationic hexanuclear niobium [Nb Cl (H O) ] cluster complex in aqueous solutions results in a 1:1 supramolecular assembly {[Nb Cl (H O) ]@γ-CD} . NMR spectroscopy, isothermal titration calorimetry (ITC), and ESI-MS were used to study the interaction between the inorganic cluster and the organic macrocycle. Such molecular association affects the biological activity of [Nb Cl (H O) ] , decreasing its cytotoxicity despite enhanced cellular uptake. The 1:1 stoichiometry is maintained in solution over a large window of the reagents' ratio, but crystallization by slow evaporation produces a 1:2 host-guest complex [Nb Cl (H O) @(γ-CD) ]Cl ⋅20 H O featuring the cluster encapsulated between two molecules of γ-CD. The 1:2 complex was characterized by XRD, elemental analysis, IR spectroscopy, and thermogravimetric analysis (TGA). Quantum chemical calculations were performed to model host-guest interaction.
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http://dx.doi.org/10.1002/chem.202000739DOI Listing
June 2020

One- and Two-Dimensional Iodine-Rich Iodobismuthate(III) Complexes: Structure, Optical Properties, and Features of Halogen Bonding in the Solid State.

Inorg Chem 2020 Mar 10;59(5):3290-3296. Epub 2020 Feb 10.

Nikolaev Institute of Inorganic Chemistry SB RAS, Lavrentieva St. 3, 630090 Novosibirsk, Russia.

Reactions of BiI, I, and iodide salts of two different pyridinum cations result in the formation of the novel iodine-rich iodobismuthates(III) (1,3-MePy){[BiI](I)} () and (1-MePy){[BiI](I)) (), where the halometalate anions are connected by diiodine linkers into one- or two-dimensional supramolecular structures. Both complexes reveal narrow optical band gaps and fairly high thermal stability, favoring their potential use in photovoltaic devices.
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http://dx.doi.org/10.1021/acs.inorgchem.9b03734DOI Listing
March 2020

Is It Possible To Prepare a Heterometal Anderson-Evans Type Anion?

Inorg Chem 2020 Feb 24;59(4):2116-2120. Epub 2020 Jan 24.

Nikolaev Institute of Inorganic Chemistry SB RAS , 3 Akad. Lavrentiev Avenue , 630090 Novosibirsk , Russia.

Reaction of [SbWO] with [Pt(HO)(OH)] results in the first example of the mixed addenda Anderson-Evans type Pt{Sb(OH)}WO] anion, isolated and characterized as KNa[Pt{Sb(OH)}WO](NO)(OH)11HO ().
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http://dx.doi.org/10.1021/acs.inorgchem.9b02898DOI Listing
February 2020

Self-Assembly of Ag/[PWNbO] Complexes in Nonaqueous Solutions.

Inorg Chem 2020 Feb 22;59(3):1853-1862. Epub 2020 Jan 22.

Nikolaev Institute of Inorganic Chemistry , 3 Akad. Lavrentiev Avenue , 630090 Novosibirsk , Russia.

Self-assembly between Ag and [PWNbO] in N- and O-donor solvents (nitriles and amides) has been studied. In the case of dimethylformamide (DMF), formation of a yellow [Ag(DMF)][PWNbO] () metastable phase and a colorless [Ag(DMF)][PWNbO] () stable phase was observed. In acetonitrile (CHCN), the product was [Ag(CHCN)]{[Ag(CHCN)][PWNbO]} (). By contrast, [SiWO] of the same size and charge as [PWNbO] produces [Ag(CHCN)][SiWO] (). Partial desolvation of and leads to Ag[PWNbO]·7.5CHCN () and Ag[SiWO]·7.5CHCN (), respectively. The CHCN molecules in the structure of are labile, and this compound was used as the starting material to study solvent-exchange processes in -methyl-2-pyrrolidone (NMP), dimethylacetamide (DMA), diethylformamide (DEF), and benzonitrile (PhCN) solutions. These solvent reactions yield [Ag(DMA)][Ag(DMA)][PWNbO] (), [Ag(NMP)(CHCN)][PWNbO]·1.3NMP (), [Ag(NMP)][PWNbO] (), Ag[PWNbO]·9.5DEF (), and [Ag(PhCN)][{Ag(PhCN)}PWNbO] (). All products were isolated and characterized by single-crystal X-ray diffraction (except for and ), IR, elemental analysis, and thermogravimetric analysis techniques. The O-donor solvents favor polynuclear, solvent-bridged cationic aggregates. In the case of DMF, DMA, and DEF discrete, tri- and tetranuclear polycations are observed, while in the case of NMP, the formation of infinite polycationic structures takes place. By contrast, the N-donor solvents (CHCN and PhCN) favor mononuclear cations, which can exist either as distorted tetrahedral, isolated [Ag(Solv)] cations or as pseudotriangular {Ag(Solv)} units, additionally coordinated to a polyoxometalate. Screening of the luminescent properties for solid samples of - revealed that only / and are emissive. In particular, the sample containing and demonstrates long-lived phosphorescence with a 30 ms lifetime.
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http://dx.doi.org/10.1021/acs.inorgchem.9b03064DOI Listing
February 2020

[{AgL}MoO] complexes: a combined experimental and theoretical study.

Dalton Trans 2020 Feb 13;49(5):1522-1530. Epub 2020 Jan 13.

Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Akad. Lavrentiev Ave, 630090 Novosibirsk, Russia. and Novosibirsk State University, 2 Pirogova Str., 630090 Novosibirsk, Russia.

Self-assembly reactions between AgNO, L (PPh, PPhPy, AsPh, SbPh) and [β-MoO] in DMF led to the formation of [β-{AgL}MoO] anions, which were isolated as BuN salts (1-4) and characterized by XRD, IR and elemental analysis. In the crystal structures Ag can switch the coordination number from 5 (P, As) to 6 (Sb) by uptake of a DMF molecule. High-level QAIM analysis of the coordination sphere around Ag shows critical points even in the case of longer Ag-O distances. Changing the ligand type to a family of substituted pyridines results in novel Ag-L-POM complexes with different environments around Ag. For 3-X-pyridine ligands (X = Cl, Br, I), complexes with additional DMF molecules [β-{AgL(DMF)}MoO] (5-7) have been isolated. Halogen bonding of the XO type was detected in the crystal structures of 5-7 and studied by DFT calculations, providing estimated energies from 0.9 to 3.4 kcal mol. Variation of substituents at the pyridine ring results in the formation of [β-{AgL}MoO] in the case of 2-NH-py (8), 2-CH-Py (9), 2,4,6-collidine (10) and 2,6-NH-py (11). Solution behavior of 1-4 in CHCN was studied by a hyphenated HPLC-ICP-AES technique. According to the results, the [β-{AgL}MoO] anions are largely dissociated in this medium. An attempt to change the [MoO] precursor to [MoO] (in the case of AgNO and PyPPh) resulted in the crystallization of [Ag(PyPPh)(DMF)][MoO] (12).
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http://dx.doi.org/10.1039/c9dt04043aDOI Listing
February 2020

Reactions of [Ru(NO)Cl] with pseudotrilacunary {XWO} (X = As, Sb) anions.

Dalton Trans 2019 Nov 9;48(42):15989-15999. Epub 2019 Oct 9.

Nikolaev Institute of Inorganic Chemistry, 3 Akad. Lavrentiev Ave, 630090, Novosibirsk, Russia. and Novosibirsk State University, Pirogova str. 2, 630090, Novosibirsk, Russia.

Reactions of [Ru(NO)Cl] with pseudotrivacant B-α-[XWO] (X = As, Sb) at 160 °C result in the rearrangement of polyoxometalate backbones into {XM} structures. In the case of arsenic, oxidation of As to As takes place with the formation of a mixture of plenary and monosubstituted Dawson [AsWO] and [AsWRu(NO)O] anions, of which the latter was isolated as MeNH (DMA-1a and DMA-1b) and BuN (BuN-1) salts and fully characterized. Both α and α isomers of [AsWRu(NO)O] were present in the reaction mixture; pure [α-AsWRu(NO)O] was isolated as the BuN salt. In the case of antimony, [SbWO] is converted into a mixture of [SbWO] and [SbW{Ru(NO)}O]. The formation of trisubstituted [SbW{Ru(NO)}O] as a minor byproduct was detected by HPLC-ICP-AES. The monosubstituted [SbW{Ru(NO)}O] anion was isolated as DMAH (DMA-2) and mixed inorganic cation (CsKNa-2) salts and characterized by XRD, HPLC-ICP-AES, EA and TGA techniques. X-ray analysis shows the presence of the {Ru(NO)}-group in the 6-membered ("equatorial") belt of the Sb-free hemisphere. The experimental findings were confirmed and interpreted by means of quantum chemical calculations.
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http://dx.doi.org/10.1039/c9dt03328aDOI Listing
November 2019

Interaction of Hydrophobic Tungsten Cluster Complexes with a Phospholipid Bilayer.

J Phys Chem B 2019 10 2;123(41):8829-8837. Epub 2019 Oct 2.

Nikolaev Institute of Inorganic Chemistry, SB RAS , 3, Lavrentiev Ave. , Novosibirsk 630090 , Russia.

Nanoconstructions composed of lipid vesicles and inorganic units (nanoparticles, metal complexes) arouse much interest across materials science and nanotechnology as hybrid materials combining useful functionalities from both parts. Ideally, these units are to be embedded into the bilayer to keep the biophysical performance of lipid vesicles having inorganic moieties screened from the environment. This can be achieved by doping a lipid bilayer with cluster complexes of transition metals. In this work, we report the preparation of nanoparticles from trinuclear WS cluster complexes and egg phosphatidylcholine. A systematic study of their properties was performed by the differential scanning calorimetry, NMR spectroscopy, dynamic light scattering, and transmission electron microscopy. Phospholipids and clusters have been found to spontaneously self-assemble into novel cluster-lipid hybrid materials. The behavior of clusters in the hydrophobic lipid environment is determined by the structure of the ligands and cluster-to-lipid ratio. Intact cluster complexes bearing compact hydrophobic ligands are embedded into the hydrophobic midplane of a lipid bilayer, whereas cluster complexes bearing larger ligands drive the aggregation of lipids and cluster complexes. Considering these differences, it could be possible to obtain different self-assembled associates such as cluster-doped liposomes or lipid-covered crystals. These cluster-lipid hybrids can be a platform for the design of new materials for nanotechnology.
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http://dx.doi.org/10.1021/acs.jpcb.9b06006DOI Listing
October 2019

Photoactive Hexanuclear Molybdenum Nanoclusters Embedded in Molecular Organogels.

Inorg Chem 2019 Jul 5;58(14):8900-8905. Epub 2019 Jul 5.

Departamento de Química Inorgánica y Orgánica , Universitat Jaume I , Avenida Sos Baynat s/n , Castellón 12071 , Spain.

Hexanuclear molybdenum clusters are attractive species because of their outstanding photonic properties, and in the past they have been attached to a variety of supports such as organic polymers and inorganic nanoparticles, as described in the recent literature. Here, a cluster of the formula TBA[MoIAc] (TBA = tetrabutylammonium; Ac = acetate) has been supported on molecular organogels for the first time, resulting in a new soft material with remarkable photoactivity. Electron and confocal microscopic analyses showed the alignment of the nanoclusters to 1D self-assembled fibers formed by the organic gelator, and emission spectroscopy corroborated the interaction of the emissive clusters with such fibrillary structures. The new hybrid system is a deep-red emissive material (phosphorescence maximum at ca. 680 nm), with chromatic coordinates = 0.725 and = 0.274, capable of efficiently generating singlet oxygen (O) upon illumination with white light, as demonstrated by the photooxygenation of 9,10-dimethylanthracene and 1,5-dihydroxynaphthalene. The organogels can been made in dichloromethane and toluene and in both solvents display phosphorescence emission and photocatalytic properties.
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http://dx.doi.org/10.1021/acs.inorgchem.9b00916DOI Listing
July 2019

Octahedral {TaI} Clusters.

Inorg Chem 2019 Jul 24;58(14):9028-9035. Epub 2019 Jun 24.

Nikolaev Institute of Inorganic Chemistry SB RAS , 3 Akad. Lavrentiev Ave. , Novosibirsk 630090 , Russian Federation.

Ta powder reacts with I at 650 °C with the formation of TaI, which belongs to the family of {M(μ-X)} clusters. It undergoes aquation with the formation of the intensely colored [TaI(HO)]. The crystal structure was determined for [TaI(HO)](BPh)·HO (Ta-Ta 2.9322(6) Å, Ta-I 2.8104(7) Å, Ta-O 2.3430(5) Å). With DMF, [TaI(DMF)]I·DMF was isolated (Ta-Ta 2.9500(2) Å, Ta-I 2.8310(4) Å, Ta-O 2.2880(7) Å). Cyclic voltammetry of [TaI(HO)] shows two consecutive quasi-reversible one-electron oxidations ( 0.61 and 0.92 V vs Ag/AgCl). Reaction of TaI with BuNCN yields (BuN)[TaI(CN)]·CHCN (Ta-Ta 2.9777(4) Å, Ta-I 2.8165(6) Å, Ta-C 2.2730(7) Å). Quantum chemical calculations reproduce well the experimental geometry of the aqua complex and show the essentially Ta-centered nature of both the HOMO and LUMO. The long-term stability of [TaI(HO)] solutions can be greatly enhanced in the presence of polystyrenesulfonate (PSS), which forms nanoparticle associates with the aqua complex in water (ca. 1 cluster per 3 PSS monomeric units).
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http://dx.doi.org/10.1021/acs.inorgchem.9b00364DOI Listing
July 2019

Hybrid organic-inorganic supramolecular systems based on a pyridine end-decorated molybdenum(ii) halide cluster and zinc(ii) porphyrinate.

Dalton Trans 2019 Feb 16;48(5):1835-1842. Epub 2019 Jan 16.

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr. 31-4, Moscow, 119071, Russia. and Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky pr. 31, Moscow, 119991, Russia.

Herein, first examples of supramolecular hybrid organic-inorganic cluster-porphyrin [CP (n = 2, 6)] systems constructed via metal-ligand coordination have been reported. The pyridine end-decorated Mo(ii) halide cluster ((BuN)[{MoI}(OOC-CHN)]), possessing remarkable photophysical properties, was chosen as the inorganic part and A-type zinc porphyrin 5,15-bis[(p-tolyl)porphyrinato(2-)]zinc was selected as the organic part. The crystal structures of CP and CP hybrids have been characterised by single crystal X-ray diffraction. The CP complex is composed of two zinc porphyrins, coordinated to pyridyl moieties of the same cluster molecule, related by an inversion center. In the case of the CP complex, each cluster has three pairs of coordinated symmetrically equivalent zinc porphyrins. Also, the formation of supramolecular hybrid CP (n = 2, 6) systems was unambiguously demonstrated in solution via NMR and UV-Vis spectroscopy titration and diffusion ordered NMR spectroscopy (DOSY).
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http://dx.doi.org/10.1039/c8dt04452jDOI Listing
February 2019
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