Luminescence and Generation of Reactive Oxygen Species in Solution by TaBr Clusters.

An intrinsic metal cluster NIR-II emission of the {TaBr} aqua/hydroxocomplexes was determined in aqueous solutions under inert atmosphere. The photoluminescence (PL) is enhanced in DO, and the lifetime scale expands from nanoseconds to microseconds. Possible cluster emission transitions have been assigned and analyzed from a computational perspective.

Discrete Hexa- and Binuclear Heterometallic Iodobismuthate(III) Complexes with Cu(I) and Ag(I).

The rare examples of discrete anionic halobismuthates(III) with group 11 elements were obtained. Those are (3-MePyH)[BiCuI] () and (3,5-MePyC)[BiAgI] () (3-MePyH = 3-methylpyridinium cation, 3,5-MePyC=1,6-bis(3,5-dimethylpyridinium)hexane dication). Both complexes were isolated as pure phases; the optical band gaps for and are 1.

Iodine-Rich Supramolecular Complexes of Chlorobismuthates(III): Unusual Lone Pair Activity and Features of Halogen Bonding in Crystals.

The first chrorobismuthate(III) supramolecular hybrids with halogen-bond-linked I, (Py(CH)Py){[BiCl](I)} () and (Py(CH)Py){[BiCl](I)} (), were synthesized via the reaction between BiO, I, and salts of the corresponding cations in HCl. The compounds featured one- and two-dimensional (2D) supramolecular motifs built by I···Cl contacts; in the case of , Bi(III) is pentacoordinated due to the lone pair activity, which also interacted with I pi-orbitals, as confirmed by density functional theory (DFT) calculations. Both complexes exhibited moderate thermal stabilities and relatively narrow optical band gaps.

Noncovalent Dualism in Perylene-Diimide-Based Keggin Anion Complexes: Theoretical and Experimental studies.

We report the synthesis and comprehensive characterization of organic-inorganic hybrid salts formed by bis-cationic bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD) and Keggin-type [XWO] (X = Si, = 4; X = P, = 3) polyoxometalates. (PTCD)[PWO]·3DMSO·2HO () and (PTCD)[SiWO]·DMSO·2HO () were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π-π interactions, contrasting with the previously reported cation-anion stacking observed in naphthalene diimide derivatives.

Copper and silver heterometallic iodoantimonates: structure, thermal stability, and optical properties.

Seven heterometallic iodoantimonates with the general formula (Cat){[SbMI]} (M = Cu(I) (1-6), Ag(I) (7)) were prepared. X-ray diffraction data indicate that these compounds are the first Sb(III) representatives of the structural type previously known only for heterometallic iodobismuthates(III). In 3 and 4, halogen-substituted cations form halogen bonds with the heterometallic halometalate chain.

Octahedral Tantalum Bromide Clusters as Catalysts for Light-Driven Hydrogen Evolution.

The development of an efficient hydrogen generation strategy from aqueous protons using sunlight is a current challenge aimed at the production of low-cost, easily accessible, renewable molecular hydrogen. For achieving this goal, non-noble metal containing and highly active catalysts for the hydrogen evolution reaction (HER) are desirable. Octahedral tantalum halide clusters {Ta(μ-X)} (X = halogen) represent an emerging class of such HER photocatalysts.

Not So Similar: Different Ways of Nb(V) and Ta(V) Catecholate Complexation.

The reactions between catechol (Hcat) and niobium(V) or tantalum(V) precursors in basic aqueous solutions lead to the formation of catecholate complexes of different natures. The following complexes were isolated and characterized by single-crystal X-ray diffraction (SCXRD): () (NH)[NbO(cat)]∙4HO; () K[Nb(cat)(Hcat)]·2Hcat·2HO; () Cs[NbO(cat)]·HO; () (NH)[TaO(cat)]·3HO; () Cs[Ta(cat)(Hcat)]·Hcat; () Cs[TaO(cat)]·7HO. The isolated crystalline products were characterized by elemental analysis, X-ray powder diffraction (XRPD), FTIR, and TGA.

Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry.

A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] (), [Ir(cod)(NO)(dpp-bian)](BF) () and [Ir(cod)(dpp-bian)](BF) (), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of - feature a square planar backbone consisting of two C = C π-bonds of 1,5-cyclooctadiene (cod) and two nitrogen atoms of dpp-bian supplemented with a chloride ion (for ) or a NO group (for ) to complete a square-pyramidal geometry. In the nitrosyl complex , the Ir-N-O group has a bent geometry (the angle is 125°).

NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions.

Solution behavior of K;[(Mn(HO))PWO]·7HO (), Na(NH)H[(Mn(HO))(WO(HO))(α-B-SbWO)]·27HO (), and NaH[(Mn(HO))(WO)(β-B-TeWO)]·19HO () was studied with NMR-relaxometry and HPLC-ICP-AES (High Performance Liquid Chromatography coupled with Inductively Coupled Plasma Atomic Emission Spectroscopy). According to the data, the [(Mn(HO))PWO] Keggin-type anion is the most stable in water among the tested complexes, even in the presence of ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA). Aqueous solutions of and anions are less stable and contain other species resulting from dissociation of Mn.

Copper- and Silver-Containing Heterometallic Iodobismuthates: Features of Thermochromic Behavior.

Nine heterometallic iodobismuthates with the general formula Cat{[BiMI}] (M = Cu(I), Ag(I), Cat = organic cation) were synthesized. According to X-ray diffraction data, their crystal structures consisted of {BiI} units interconnected with Cu(I) or Ag(I) atoms through I-bridging ligands, forming one-dimensional polymers. The compounds are thermally stable up to 200 °C.

Supramolecular hybrids based on Ru(II) porphyrin and octahedral Mo(II) iodide cluster.

The coordination-driven design and synthesis of new stable supramolecular cluster-porphyrin (CP) hybrids based on an A-type ruthenium porphyrin 5,15-bis[(-tolyl)porphyrinato(2-)]ruthenium(carbonyl)(aqua) [RuDTolP(CO)H2O] and an octahedral molybdenum(II) iodide cluster with six terminal isonicotinate ligands (BuN)[{MoI}(OOC-CHN)] (PyMoC) are reported. The stepwise supramolecular assembly of the PyMoC "superoctahedron" with RuDTolP(CO)H2O has been studied by H NMR and 2D H-H COSY, H-N HMBC and DOSY techniques, as well as by UV-vis spectroscopy and HR-ESI mass spectrometry. The formation of discrete cluster-porphyrin CPn adducts with different numbers of coordinated porphyrins ( = 1-6), including the geometrical isomers of CP2, CP3 and CP4, has been observed.

One-Dimensional Iodoantimonate(III) and Iodobismuthate(III) Supramolecular Hybrids with Diiodine: Structural Features, Stability and Optical Properties.

Two isostructural pairs of supramolecular iodoantimonate(III) and iodobismuthate(III) complexes with I units "trapped" in solid state via halogen bonding-Cat[[MI](I)} (Cat = tetramethylammonium and 1-methylpyridinium, M = Sb(III) and Bi(III)) were prepared. For all compounds, values of optical band gaps were determined, together with thermal stability; the complexes were additionally characterized by Raman spectroscopy.

Proton Affinity in the Chemistry of Beta-Octamolybdate: HPLC-ICP-AES, NMR and Structural Studies.

The affinity of [β-MoO] toward different proton sources has been studied in various conditions. The proposed sites for proton coordination were highlighted with single crystal X-ray diffraction (SCXRD) analysis of (BuN)[β-{Ag(py-NH)MoO]}] () and from analysis of reported structures. Structural rearrangement of [β-MoO] as a direct response to protonation was studied in solution with Mo NMR and HPLC-ICP-AES techniques.

Nanostructured Hybrids Based on Tantalum Bromide Octahedral Clusters and Graphene Oxide for Photocatalytic Hydrogen Evolution.

The generation of hydrogen (H) using sunlight has become an essential energy alternative for decarbonization. The need for functional nanohybrid materials based on photo- and electroactive materials and accessible raw materials is high in the field of solar fuels. To reach this goal, single-step synthesis of {TaBr}@GO (GO = graphene oxide) nanohybrids was developed by immobilization of [{TaBr}Br(HO)]·4HO (i = inner and a = apical positions of the Ta octahedron) on GO nanosheets by taking the advantage of the easy ligand exchange of the apical cluster ligands with the oxygen functionalities of GO.

Trapping of Ag into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry.

Self-assembly of (BuN)[β-MoO], AgNO, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (BuN)[β-{Ag(dpp-bian)}MoO] () complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding.

Coordination of Pt(IV) by {PW} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies.

Hydrothermal reaction of a macrocyclic inorganic POM cavitand Li(NH)H[PWO] with [Pt(HO)(OH)] results in coordination of up to six {Pt(HO)(OH)} fragments to the internal surface of the polyoxoanion. The product was isolated as K(NH)H[{Pt(OH)(HO)}PWO]·79HO () and characterized by multiple techniques in the solid state (SCXRD, XRPD, XPS, FTIR, and TGA) and in solution (NMR, ESI-MS, and HPLC-ICP-AES). Electrochemical properties were studied both in solution and as components of the paste electrode.

Selenium(IV) Polybromide Complexes: Structural Diversity Driven by Halogen and Chalcogen Bonding.

Reactions between bromoselenate(IV)-containing solutions, dibromine and salts of pyridinium-family organic cations resulted in structurally diverse, bromine-rich polybromine-bromoselenates(IV): (4-MePyH)[SeBr][SeBr](Br) (), (2-MePyH){[SeBr](Br)} (), (PyH){[SeBr]Br(Br)} (), (1-MePy){[SeBr](Br)} (). The compounds feature halogen and (in the case of ) chalcogen bonding in solid state, resulting in formation of supramolecular architectures of different dimensionality. DFT calculations allowed estimation of the energies of non-covalent interactions in -; additionally, characterization by Raman spectroscopy was performed.

Supramolecular Diiodine-Bromostannate(IV) Complexes: Narrow Bandgap Semiconductors.

Three supramolecular bromostannates(IV) with "trapped" diiodine molecules, Cat{[SnBr](I)} (Cat = MeN (), 1-MePy () and 4-MePyH ()), were synthesized. In all cases, I linkers are connected with bromide ligands via halogen···halogen non-covalent interactions. Articles were studied using Raman spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy.

Sterically Hindered Tellurium(IV) Catecholate as a Lewis Acid.

Sterically hindered tellurium catecholate Te(Cat) (Cat = 3,6-di--butyl-catecholate) was synthesized with the reaction of amorphous Te with 3,6-di--butyl--benzoquinone. Adducts of Te(Cat) with various O- and N-donors were isolated and characterized by means of single-crystal X-ray diffraction along with IR, UV-vis, and NMR (H, C, and Te) spectroscopies. In the crystal structure of the adduct with 2,2'-bipyridine (bipy), the unprecedented μ-κ,':κ,'-bridging coordination mode of bipy was observed.

Zn(II) and Co(II) 3D Coordination Polymers Based on 2-Iodoterephtalic Acid and 1,2-bis(4-pyridyl)ethane: Structures and Sorption Properties.

Metal-organic frameworks [M(2-I-bdc)bpe] (M = Zn(II) (), Co(II) (), 2-I-bdc = 2-iodoterephtalic acid, and bpe = 1,2-bis(4-pyridyl)ethane) were prepared and characterized by X-ray diffractometry. Both compounds retain their 3D structure after the removal of guest DMF molecules. Selectivity of sorption of different organic substrates from the gas phase was investigated for both complexes.

Heteroleptic Pd(II) and Pt(II) Complexes with Redox-Active Ligands: Synthesis, Structure, and Multimodal Anticancer Mechanism.

A series of heteroleptic square-planar Pt and Pd complexes with bis(diisopropylphenyl) iminoacenaphtene (dpp-Bian) and Cl, 1,3-dithia-2-thione-4,5-dithiolate (dmit), or 1,3-dithia-2-thione-4,5-diselenolate (dsit) ligands have been prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis, and cyclic voltammetry (CV). The intermolecular noncovalent interactions in the crystal structures were assessed by density functional theory (DFT) calculations. The anticancer activity of Pd complexes in breast cancer cell lines was limited by their solubility.

Self-assembly patterns of non-metalloid silver thiolates: structural, HR-ESI-MS and stability studies.

Screening of AgNO/AgSBu solutions in DMF, DMSO and NMP resulted in the isolation of three novel nanosized silver/thiolate complexes with a torus-like {Ag(SBu)} core. The structures of [NO@Ag(SBu)(NO)(DMF)] (1) and [NO@Ag(BuS)(NO)(NMP)][NO@Ag(BuS)(NO)(NMP)](NO) (2) were studied by single crystal X-ray diffraction (SCXRD). The self-assembly process leading to 1 can be switched to a different outcome using Br, resulting in [Br@Ag(SBu)(NO)(DMF)](NO) (3), which is the one of the few genuine host-guest complexes in the silver/thiolate systems.

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

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.

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

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.