Tungsten oxide as a universal source for the synthesis of complexes with different nuclearities in WO/chalcogen/NaCN systems.

Tungsten trioxide can be used as a readily available source in the one-step preparation of a variety of cyanide and chalcocyanide mononuclear and cluster complexes of tungsten. In our study of phase formation in the system 6WO + 8Q + 32NaCN (Q = S, Se or Te) in the temperature range of 250-700 °C, we determined which soluble complex compounds are formed, the temperature limits of their existence and the influence of synthesis time on the composition of the products. As the temperature increases, the process begins with the formation of mononuclear and then cluster complexes and ends with the formation of tungsten dichalcogenides: [W(CN)] → [WS]/[WSO] → [{WQ}(CN)] (Q = S or Se), [{WSO}(CN)] → [{WQ}(CN)] (Q = S, Se or Te) → WQ (Q = S or Se).

Emissive supramolecular ionic crystals combining a red-NIR phosphorescent [ReSeCN] cluster anion and a blue fluorescent tetraphenylethene counter-cation.

A blue fluorescent tetraphenylethylene-based dication and a red-NIR phosphorescent rhenium octahedral cluster tetra-anion are associated electrostatically to generate a supramolecular ionic framework which crystallizes in the 1̄ centric space group. The emission properties of the hybrids are studied in the crystalline state and in solution revealing a resonant energy transfer and a high sensitivity toward oxygen.

Luminescent Supramolecular Ionic Frameworks based on Organic Fluorescent Polycations and Polyanionic Phosphorescent Metal Clusters.

Emissive ionic supramolecular frameworks are designed by associating tetraphenylethylene-based tetra-cationic units and di-anionic molybdenum or tetra-anionic rhenium octahedral clusters. Obtained structures were characterized by single-crystal X-ray diffraction. The emission properties of the hybrids were investigated as dry powders or in various solvents by one photon and two photon absorption leading to a O concentration dependent luminescence color for the Mo based hybrid.

In-Situ Electrochemical Exfoliation and Methylation of Black Phosphorus into Functionalized Phosphorene Nanosheets.

Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most of the methods for BP functionalization with organic substrates require either the use of low-stable precursors of highly reactive intermediates or the use of difficult-to-manufacture and flammable BP intercalates.

Octahedral Rhenium Cluster Complexes with 1,2-Bis(4-pyridyl)ethylene and 1,3-Bis(4-pyridyl)propane as Apical Ligands.

A series of eight new octahedral rhenium cluster complexes with the general formula -[{ReQ}LX] (Q = S or Se; L = 1,2-Bis(4-pyridyl)ethylene (bpe) or 1,3-Bis(4-pyridyl)propane (bpp); X = Cl or Br) was synthesized and investigated. While bpe is a ligand with a conjugated aromatic system, bpp represents a molecule of opposite type and has independent aromatic systems of the two pyridine rings. It was shown that this difference in the electronic structure of the ligands has a fundamental effect on the electronic structure, electrochemical and luminescent properties of the corresponding cluster complexes.

Coordination Polymers Based on Rhenium Octahedral Chalcocyanide Cluster Anions and Ag Cations with Bipyridine Analogs.

A series of six coordination polymers based on octahedral cluster anions [ReQ(CN)] (Q = S or Se) and Ag cations coordinated by bipyridine analogs were synthesized under solvothermal conditions. Their structures have been characterized by single crystal X-ray diffraction. Compounds and described by the general formula [{Ag(phen)}ReQ(CN)] (Q = Se (), S (); phen = 1,10-phenanthroline) exhibit layered structures assembled into a supramolecular network by CH…π contacts.

The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and N NMR Studies of [{Re(μ-X)}(N)] (X = Br or I).

Azide cluster complexes [{Re(μ-Br)}(N)] and [{Re(-I)}(N)] were obtained by reaction of ReX (X = Br or I, respectively) with sodium azide in methanol. The complexes were crystallized as cesium salts of the compositions Cs[{Re(μ-Br)}(N)]·HO () and Cs[{Re(μ-I)}(N)]·HO () and characterized by X-ray single-crystal diffraction and elemental analyses, mass spectrometry, N NMR spectroscopy, and DFT calculations. In the anions, each rhenium atom is coordinated by three azide ligands.

Molecular and Nano-Structural Optimization of Nanoparticulate Mn-Hexarhenium Cluster Complexes for Optimal Balance of High T- and T-Weighted Contrast Ability with Low Hemoagglutination and Cytotoxicity.

The present work introduces rational design of nanoparticulate Mn(II)-based contrast agents through both variation of the μ (inner) ligands within a series of hexarhenium cluster complexes [{Re(μ-Q)}(CN)] (ReQ, Q = S, Se or Te) and interfacial decoration of the nanoparticles (NPs) KMnReQ ( = 1.3 - 1.8) by a series of pluronics (F-68, P-123, F-127).

New Approach toward Dual-Emissive Organic-Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals.

Inorganic-organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general "Mn + Cu" approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn(O∧O)] cations and various anionic [CuI] clusters, ensuring manifestation of dual phosphorescence streamed from octahedral Mn ions (605-648 nm) and iodocuprate anions (480-728 nm).

Intense multi-colored luminescence in a series of rare-earth metal-organic frameworks with aliphatic linkers.

Two series of highly luminescent yttrium(iii), europium(iii) and terbium(iii) metal-organic frameworks containing diimine aromatic ligands and the dicarboxylate linker trans-1,4-cyclohexanedicarboxylate (chdc) which can be described by the general formulas [M(bpy)(chdc)], where M = Y (1), Eu (2), and Tb (3) and bpy = 2,2'-bipyridyl, and [M(phen)(chdc)], where M = Y (4), Eu (5), and Tb (6) and phen = 1,10-phenanthroline, were synthesized and characterized. All compounds are based on the same dinuclear {M(L)(OOCR)} building blocks and possess a similar topology of the 3D framework with narrow pores. The chelate aromatic ligands act as efficient light-harvesting antennas for subsequent energy transfer to the emitting metal center (M = Eu, Tb) or intraligand photoemission (M = Y).

Cyanide Complexes Based on {MoI} and {WI} Cluster Cores.

Compounds based on new cyanide cluster anions [{MoI}(CN)], -[{MoI}(CN)(MeO)] and -[{WI}(CN)(MeO)] were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {MoI} and {WI} cores do.

Soluble Molecular Rhenium Cluster Complexes Exhibiting Multistage Terminal Ligands Reduction.

Substitution of terminal halide ligands of octahedral rhenium cluster complexes [ReQX] in a melt of 4,4'-bipyridine (bpy) led to us obtaining four new compounds with the general formula -[ReQ(bpy)X] (Q = S or Se; X = Cl or Br) in high yield. In contrast to most of the known molecular rhenium cluster complexes with heteroaromatic terminal ligands, compounds - are soluble in organic solvents. This made it possible to carry out a detailed characterization of the new compounds both in solids and in solutions.

The first example of the stereoselective synthesis and crystal structure of a spirobicycloquinazolinone based on (-)-fenchone and anthranilamide.

The possibility of a single-stage solvent-free stereoselective synthesis of a spirocyclic compound from the natural bicyclic monoterpenoid (-)-fenchone and anthranilamide has been shown for the first time. The molecular and crystal structure of (1R,2S,4S)-1,3,3-trimethyl-1'H-spiro[bicyclo[2.2.

[{ReQ}(SO)] (Q = S or Se): Facile Synthesis and Properties of the Most Highly Charged Octahedral Cluster Complexes and High Magnetic Relaxivity of Their Colloids with Gd Ions.

New octahedral rhenium cluster complexes [{ReQ}(SO)] (Q = S or Se) were synthesized starting from [{ReQ}(HO)(OH)]·12HO. The complexes were crystallized as sodium salts and characterized by X-ray single-crystal diffraction and elemental analyses, IR, UV/vis and luminescence spectroscopies. Magnetic relaxation data demonstrate the complex formation of the cluster units with gadolinium ions.

Luminescent twelve-nuclear rhenium clusters.

The first luminescent twelve-nuclear rhenium cluster complexes were obtained. Three new clusters, namely, [ReCS(μ-Cl)Cl], [ReCS(μ-Br)Cl] and [ReCS(μ-Br)Br], were synthesized using the non-isovalent substitution of μ-O ligands within the {ReCS(μ-O)} cluster core by halide anions. The geometry of the new clusters was investigated by X-ray structural analysis, and the electronic structures were evaluated by the use of DFT calculations.

Host-Guest Binding Hierarchy within Redox- and Luminescence-Responsive Supramolecular Self-Assembly Based on Chalcogenide Clusters and γ-Cyclodextrin.

Water-soluble salts of anionic [Re Q (CN) ] (Q=S, Se, Te) chalcogenide octahedral rhenium clusters react with γ-cyclodextrin (γ-CD) producing a new type of inclusion compounds. Crystal structures determined through single-crystal X-ray diffraction analysis revealed supramolecular host-guest assemblies resulting from close encapsulations of the octahedral cluster within two γ-CDs. Interestingly, nature of the inner Q ligands influences strongly the host-guest conformation.

A comparative study of hydrophilic phosphine hexanuclear rhenium cluster complexes' toxicity.

The octahedral rhenium cluster compound NaH[{ReSe}(P(CHCONH)(CHCOO))] has recently emerged as a very promising X-ray contrast agent for biomedical applications. However, the synthesis of this compound is rather challenging due to the difficulty in controlling the hydrolysis of the initial P(CHCN) ligand during the reaction process. Therefore, in this report we compare the and toxicity of NaH[{ReSe}(P(CHCONH)(CHCOO))] with those of related compounds featuring the fully hydrolysed form of the phosphine ligand, namely NaH[{ReQ}(P(CHCOO))] (Q = S or Se).

Nanosized mesoporous metal-organic framework MIL-101 as a nanocarrier for photoactive hexamolybdenum cluster compounds.

Inclusion compounds of photoluminescent hexamolybdenum cluster complexes in the chromium terephthalate metal-organic framework, MIL-101 (MIL, Matérial Institut Lavoisier) were successfully synthesized in two different ways and characterized by means of powder X-Ray diffraction, chemical analysis and nitrogen sorption. Some important functional properties of hexamolybdenum cluster complexes for biological and medical applications, in particular singlet oxygen generation ability, luminescence properties, cellular uptake behavior and cytotoxicity were studied. It was revealed that the inclusion compounds possessed significant singlet oxygen generation activity.

Octahedral molybdenum cluster complexes with aromatic sulfonate ligands.

This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (BuN)[{MoX}(OTs)] and (BuN)[{MoX}(PhSO)] (where X is Cl, Br or I; OTs is p-toluenesulfonate and PhSO is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo6I8}(4+) Core Cluster Complexes by Terminal Carboxylate Ligands.

The reactions between the tetra-n-butylammonium salt of [{Mo6I8}I6](2-) and silver carboxylates RCOOAg (R = CH3 (1), C(CH3)3 (2), α-C4H3O (3), C6H5 (4), α-C10H7 (5), or C2F5 (6)) in CH2Cl2 afforded new carboxylate complexes [{Mo6I8}(RCOO)6](2-). The complexes were characterized by X-ray single-crystal diffraction and elemental analysis, cyclic/differential pulse voltammetry, and IR, NMR, and UV-visible spectroscopies. The emission properties of the complexes 1-6, and those of the earlier reported complexes with R = CF3 (7) and n-C3F7 (8), were studied both in acetonitrile solution and in the solid state.

Cellular internalization and morphological analysis after intravenous injection of a highly hydrophilic octahedral rhenium cluster complex - a new promising X-ray contrast agent.

The octahedral cluster compound Na H [{Re Se }(P(C H CONH )(C H COO) ) ] has been shown to be highly radio dense, thus becoming a promising X-ray contrast agent. It was also shown that this compound had low cytotoxic effect in vitro, low acute toxicity in vivo and was eliminated rapidly from the body through the urinary tract. The present contribution describes a more detailed cellular internalization assay and morphological analysis after intravenous injection of this hexarhenium cluster compound at different doses.

Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {MoI} metal clusters.

Silica nanoparticles (SNPs) doped by hexanuclear molybdenum cluster complexes [{MoX}L] (X = Cl, Br, or I; L = various inorganic or organic ligands) have been recently suggested as materials with high potential for biomedical applications due to both their outstanding photoluminescence properties and their ability to efficiently generate singlet oxygen upon photoirradiation. However, no studies were undertaken so far to prove this concept. Therefore, here we examined the potential of photoluminescent SNPs doped by {MoI} for applications such as bioimaging and photodynamic therapy using the human epidermoid larynx carcinoma (Hep-2) cell line as a model.

Sensing activity of cholinesterases through a luminescence response of the hexarhenium cluster complex [{Re6S8}(OH)6](4.).

The present work describes a new method to sense cholinesterase-catalyzed hydrolysis of acetylcholine (ACh) through a luminescence response of the hexarhenium cluster complex [{Re6S8}(OH)6](4-). A proton released from acetylcholinesterase (AChE)- or butyrylcholinesterase (BuChE)-catalyzed hydrolysis of ACh results in time-resolved sensitization of cluster-centered luminescence. The sensitization results from protonation of apical hydroxo-groups of the cluster complex.

Prospects of molybdenum and rhenium octahedral cluster complexes as X-ray contrast agents.

Investigation of new X-ray contrast media for radiography is an important field of science since discovering of X-rays in 1895. Despite the wide diversity of available X-ray contrast media the toxicity, especially nephrotoxicity, is still a big problem to be solved. The octahedral metal-cluster complexes of the general formula [{M6Q8}L6] can be considered as quite promising candidates for the role of new radiocontrast media due to the high local concentration of heavy elements, high tuning ability of ligand environment and low toxicity.