The reaction of Na2-x{H}x[Mo6I8(BTA)6] with [tBuXPhos-Ag(OTf)(CH3CN)] (tBuXPhos - 2-di-tert-butylphosphino-2 ',4 ',6 '-triisopropylbiphenyl) leads to the strongly emissive solid heterometallic complex [Mo6I8(BTA-Ag(tBuXPhos))6](OTf)4.

The heating of Re3I3Br6 up to 450 degrees C led to the formation of Re3Br9. Carbonylation of Re3Br9 with HCOOH at 130 degrees & Scy; in concentrated HBr leads to the formation of Re(CO)5Br in a good yield. The formation of Re3Br9 and Re (CO)5Br was confirmed by single crystal X-ray diffraction analysis. The cluster phase Re3Br9 was characterized by powder X-ray diffraction analysis and energy-dispersive spectroscopy. Re(CO)5Br was additionally identified by energy-dispersive spectroscopy and Raman spectroscopy. New structures have been determined for an aquation product of Re3Br9, [Re3Br9(H2O)3]center dot 3Et2O, and for (PyH)2ReBr6, which was obtained as pyridinium by extraction with HBr of a by-product of the thermal decomposition of Re3I3Br6. Re3I3Br6 was characterized by thermogravimetric analysis.

Синтезирован новый 1,2,3-бензотриазолатный люминесцентный кластерный комплекс (Bu4N)2[W6I8(N3C6H4)6] (I), для сокристаллизата c 1,2,3-бензотриазолом, (Bu4N)2[W6I8(N3C6H4)6]·4(N3C6H5), установлена кристаллическая структура. По данным РСА, атомы вольфрама кластерного ядра {W6I8}4+ монодентатно координированы атомами 1-N азота 1,2,3-бензотриазолатных лигандов. Для порошкового образца нового соединения I выявлена яркая фосфоресценция c максимумом на 640 нм, значительный квантовый выход эмиссии (φ = 24%, τ = 266 мкс) в условиях контакта с кислородом воздуха является редким примером для октаэдрических кластерных комплексов типа [{M6X8}L6].

An intrinsic metal cluster NIR-II emission of the {Ta6Br12}2+ aqua/hydroxocomplexes was determined in aqueous solutions under inert atmosphere. The photoluminescence (PL) is enhanced in D2O, and the lifetime scale expands from nanoseconds to microseconds. Possible cluster emission transitions have been assigned and analyzed from a computational perspective. In the presence of O2, the cluster compound kept its robustness but showed partial quenching of the PL. Stern-Volmer and laser-flash photolysis studies confirmed that quenching is mainly associated with O2 diffusion. Laser-flash photolysis experiments showed that singlet oxygen (1O2) was not detected under measurement conditions. Generation of peroxide and superoxide radical species after irradiation in D2O was confirmed by using luminol as a probe, whereas no hydroxide radical species were detected as evidenced by the emission of the 3-coumarin carboxylic acid (3-CCA) molecular sensor.

Реакцией оксида висмута с солями различных двухзарядных катионов на основе 3,5-диметилпиридина в концентрированной HBr получены и структурно охарактеризованы комплексы {(3,5-MePy)2(CH2)n}3[Bi2Br9]2 (n = 2 (1), 5 (2). Обсуждены особенности межмолекулярных контактов в кристаллической структуре.

Four new hybrid chloroantimonates(III) and chlorobismuthates(III) with halogen bond-linked I2, (H2bpe){[MCl5](I2)} (M = Sb(III) (1); M = Bi(III) (2); bpe = 1,2-bis(4-pyridil)ethane) and (H2bpp){[MCl5](I2)} (M = Sb(III) (3); M = Bi(III) (4); bpp = 1,3-bis(4-pyridil)propane), were synthesized via a reaction between Sb2O3/Bi2O3, I2 and the corresponding bis(pyridines) in HCl. Despite sharing the same formulae of supramolecular anionic parts, they showed significant structural diversity, revealing three different structural types. Features of the halogen bond in 1-4 were examined via theoretical methods.

The reduction of Cu(NO3)2 by HStBu in CH3CN under Ar atmosphere produces a light-yellow solution containing numerous {Cux(StBu)y} species. The addition of different pyridines (py-R) into this solution results in the formation of {Cu6(StBu)4} hexanuclear complexes. The slow Et2O diffusion leads to crystals of [Cu6(StBu)4(2-Me-py)5(CH3CN)(NO3)](NO3) (1), [Cu6(StBu)4(Me3py)4(NO3)2]·3.5CH3CN (2a), [Cu6(StBu)4(Me3py)5(NO3)](NO3)·5CH3CN (2b), (NHEt3)[Cu6(StBu)4(CH3CN)3(NO3)3]·H2O (3), [Cu6(StBu)4(2-Br-py)4(NO3)2]·2-Br-Py (4), [Cu6(StBu)4(3-Br-py)6][Cu6(StBu)4(CH3CN)6](NO3)4·9CH3CN (5), and [Cu6(StBu)4(3-Cl-py)6][Cu6(StBu)4(CH3CN)6](NO3)4·5CH3CN (6). The titled compounds were characterized by single crystal X-ray diffraction (SCXRD). The Cu···Cu contacts were analyzed with quantum chemical methods.

New luminescent cluster complex (Bu4N)2[W6I8(N3C6H4)6] (I) is obtained by the reaction of (Bu4N)2[W6I8(OOCCH3)6] with 1-trimethylsilyl-1,2,3-benzotriazole (Me3Si-N3C6H4) is obtained. The crystal structure is determined for cocrystallizate I with 1,2,3-benzotriazole (Bu4N)2[W6I8(N3C6H4)6]· ·4(N3C6H5) (I·4BTA). According to single crystal X-ray diffraction data, tungsten atoms of the W6I84+ cluster core are monodentate coordinated by N1 atoms of 1,2,3-benzotriazolate ligands (average W–N distance 2.20 Å). For the powder sample of I bright phosphorescence is revealed with the emission maximum at 640 nm, φ = 24

Методом РСА на монокристаллах установлено строение трет-бутилтиолата Cu(I). Его кристаллическая структура представляет собой одномерную цепочку, составленную из тримерных звеньев [Cu3(StBu)3].

По реакции восстановления WBr6 элементарным висмутом при 280 °С получен полимерный пирамидальный кластер W5Br12•BiBr3 в виде смеси двух кластерных фаз, отличающихся между собой расположением и способом взаимодействий компонентов BiBr3 и W5Br12 в кристаллических структурах. В первой кристаллической структуре квадратно-пирамидальные кластерные фрагменты {W5Bri8}4+ связаны между собой мостиковыми атомами брома в бесконечные цепи [{W5Bri8}Bra3Bra-a2/2] взаимодействием W—Bra-a—W, во второй структуре вместо мостикового атома брома в цепь встраиваются молекулы BiBr3 (W—{BraBiBrBra}—W).

Synthesis methods, molecular and electronic structures, and reactivity of the family of the octahedral clusters of niobium and tantalum halides bearing the {M6X12} cluster core are reviewed. Possible fields of the practical use of this class of compounds are considered.

Aspects of the synthesis and isolation of (Bu4N)3[H3V10O28] (I) and Na6[V10O28]·18H2O (II) from one reaction mixture are considered. The procedure for the synthesis of compound I is optimized. The reaction of compound I and HSO3CF3 in dimethyl sulfoxide (DMSO) affords complex [VO2(DMSO)4](CF3-SO3) (III). A possibility of using complex III for the preparation of catalytically active materials based on polyethylene terephthalate (PET) is shown.

A new crystal modification of the N-heterocyclic carbene 1,3-bis(2,6-di-isopropylphenyl)-4,5-dichloroimidazol-2-ylidene (IPrCl, 1 ) is obtained and structurally characterized. The hydrolysis of this compound leads to the formation of the (IPrClH) + Cl – ( 2 ) hydrochloride. The [Co 3 (Piv) 4 Cl 2 (IPrCl) 2 ]·2C 7 H 8 ( 3 ·2C 7 H 8 ) mixed-ligand complex is synthesized by the interaction of the [Co(Piv) 2 ] n cobalt pivalate with IPrCl and is characterized by XRD.

Octahedral iodide clusters of molybdenum and tungsten [M6I8L6] are considered as promising components of new classes of luminescent materials. When excited with the light at a wavelength of ≤450 nm, the clusters form long-lived triplet states emitting red phosphorescence. This phosphorescence is deactivated in the presence of molecular oxygen to form singlet oxygen in a high yield. Due to the capability of photogenerating singlet oxygen, the [M6I8L6] clusters and related materials exhibit photoinduced cytotoxicity and bactericidal action. Universal methods developed to date make it possible to prepare cluster compounds with specified compositions and properties depending on ligand L. This review considers the prospects for developing drugs for antimicrobial photodynamic inactivation and photodynamic cancer therapy based on the [M6I8L6] clusters.

New antimony complexes, (3-Br-1-EtPy)3[Sb2I9] (1) and (1,2-Me2Py)4[Sb8I28] (2) have been prepared by the reaction of SbI3 with iodides of the corresponding cations in organic solvents. The features of the crystal structure of the compounds have been determined by X-ray diffraction. The complexes are thermally stable at least up to 200°C and have a band gap of 2.2 eV.

The present work reports the synthesis of the silica nanoparticles (SNs) incorporated by two photoactive components , which are the representatives of RuII nitrosyl complexes and [{Mo6I8}(CH3COO)6]2 � cluster units. The RuII nitrosyl complexes are incorporated through the doping procedure into the SNs. The embedding of amino-groups onto the RuII-doped SNs facilitates the deposition of the cluster units, thus, resulting in the heterometallic core-shel l SNs. Combination of the two photoactive components in the SNs results in the anti-synergistic effect on the photochemical and photodynamic activities of the RuI I and {Mo6I8}-based complexes correspondingly. The enhanced leaching of the cluster units from the heterometallic SNs correlates with the nitrosyl & RARR; nitro transformation of the encapsulated RuI I nitrosyl complexes. The formation of the so-called protein corona onto the heterometallic SNs is revealed as the reason for high colloid stability and efficientce l l internalization, which is visualized through the red emission of the {Mo6I8}-clusters. The cytotoxicity measurements reveal both synergistic effect of both components on the cytotoxicity evaluated in the so-called dark conditions and anti-synergistic effect on the photo-induced cytotoxicity. The significant dark cytotoxicity of the heterometallic SNs correlates with their high internalization and the enhanced leaching of the cluster units.

Reaction between TeO2 and I2 in HCl afforded a series of supramolecular hybrids Cat2{[TeCl6](I2)} (1–5) where diiodine fragments are linked to [TeCl6]2− octahedra via halogen bonds (XB).

Синтезированы комплексы титана с катехолатом (cat) и тетрабромокатехолатом (tbc) [K2Ti(cat)3(thf)2] (1), [K2Ti(tbc)3(dme)3] (2) и [K4Ti(tbc)3(thf)6(μ4-O)]2 (3). Комплексы охарактеризованы методом рентгеноструктурного анализа, а также ИК-спектроскопией и элементным анализом.

Four new coordination polymers based on Ln 3+ and 2,5-diiodoterephthalates (2,5-I-bdc) {[Ln 2 (2,5-I-bdc) 3 (DMF) 4 ]} —were prepared and characterized. Their luminescent properties were compared with other Ln 3+ 2,5,-I-bdc complexes; it was shown that these compounds can be used as highly effective sensors on chloro- and nitrobenzene with detection limits of 0.22 mM and 0.16 mM, respectively.

The reduction of rhenium iodide cluster Re3I9 to [Re(CO)5I] (55