Polymerisable octahedral rhenium cluster complexes as precursors for photo/electroluminescent polymers

New polymerisable photoluminescent octahedral rhenium cluster complexes trans-[{Re₆Q₈}(TBP)₄VB)₂] (Q = S or Se; TBP – p-tert-butylpyridine; VB – vinyl benzoate) have been synthesised, characterised and used to construct rhe-nium cluster-organic polymer hybrid materials. These novel polymer systems are solution-processable and the rhenium clusters retain their photoluminescent properties within the polymer environment. Notably, when the rhenium cluster complexes are incorporated into the matrix of the electroluminescent polymer poly(N-vinylcarbazole), the resultant cluster polymer hybrid combined properties of both components and was used successfully in the construc-tion of a polymer light emitting diode (PLED). These prototype devices are the first PLEDs to incorporate octahedral rhenium clusters and provide the first direct evidence of the electroluminescent properties of rhenium clusters and indeed, to the best of our knowledge, of any member of the family of 24-electron hexanuclear cluster complexes of molybdenum, tungsten or rhenium

Hexaazide octahedral molybdenum cluster complexes: synthesis, properties and the evidence of hydrolysis

This article reports the synthesis, crystal structure of new molybdenum hexaazide cluster complex (ⁿBu₄N)₂[{Mo₆I₈}(N₃)₆] (3) and comparison of its photophysical and electrochemical properties to those of earlier reported analogues (ⁿBu₄N)₂[{M₆X₈}(N₃)₆] (X = Cl, Br). Additionally, the dimerisation of 3 as a result of hydrolysis was revealed by mass spectrometry and single crystal X-Ray diffraction. Indeed, the structurally characterised compound (ⁿBu₄N)₄[{Mo₆I₈}(N₃)₅)₂O] represents the first example of oxo-bridged dimer of octahedral molybdenum clusters complexes

Advances in the Engineering of Near Infrared Emitting Liquid Crystals and Copolymers, Extended Porous Frameworks, Theranostic Tools and Molecular Junctions Using Tailored Re6 Cluster Building Blocks

International audienceAt the occasion of the fiftieth birthday of the introduction of the term 'metal atom cluster' by F. A. Cotton in inorganic chemistry, it is the good time to make a review on the advances in the engineering of molecular assemblies and nanomaterials based on octahedral Re6 metal atom clusters. The latter exhibit unique intrinsic structural and physicochemical properties (orthogonal disposition of metallic sites that can be selectively functionalized, photoluminescence, redox, generation of singlet oxygen) that make them relevant building blocks for the structuration at the nanometric scale and functionalization of hybrid organic-inorganic materials and supramolecular frameworks. After synthesis by solid state chemistry techniques at high temperature, inorganic precursors built up on face-capped [(Re6Yi8)Ya6] cluster units (Y = chalcogen and/or halogen) can be functionalized via solution chemistry techniques or organic melts to form [(Re6Yi8)La6] (L = CN, OH, various organic ligands...). This work reports advances in the synthesis of [(Re6Yi8)Ya6] and [(Re6Yi8)La6] cluster units as well as on their use in the elaboration of supramolecular frameworks, nanoparticles, hybrid nanomaterials (co-polymers and liquid crystals) and active molecular junctions

Water-soluble hybrid materials based on {Mo₆X₈}⁴⁺ (X = Cl, Br, I) cluster complexes and sodium polystyrene sulfonate

Development of water-soluble forms of octahedral molybdenum clusters {Mo₆X₈}⁴⁺ (X = Cl, Br, I) is strongly motivated by the tremendous potential that these complexes have for biological applications, namely as agents for bioimaging and photodynamic therapy. In these work we report the first water-soluble hybrid materials, which represent sodium polystyrene sulfonate doped by molybdenum clusters, and evaluation of their photophysical and biological properties (dark and photoinduced cytotoxicity and cellular uptake) with the use of cervical cancer (HeLa) and human epidermoid larynx carcinoma (Hep-2) cell-lines as models

Luminescent coordination polymers based on Ca²⁺ and octahedral cluster anions [{M₆Clⁱ₈}Clᵃ₆}²⁻ (M = Mo, W) : synthesis and thermal stability studies

Luminescent coordination polymers (CPs) based of inexpensive stable precursors are attractive materials for applications. Here we report the synthesis and evaluation of the stability and photophysical characteristics of the first examples of phosphorescent CPs based on octahedral molybdenum and tungsten cluster anions. Specifically 1D CP trans-[{Ca(OPPh₃)₄}{{M₆Clⁱ₈}Clᵃ₆}]∞ (M = Mo, W) can be obtained either directly at increased temperature or via intermediate phases [cis-Ca(OPPh₃)₄(H₂O)₂][{M₆Clⁱ₈}Clᵃ₆]∙2CH₃CN that are stable at room-temperature, but convert to the titled CP at temperatures above 100 °C

Cellular internalisation, bioimaging and dark and photodynamic cytotoxicity of silica nanoparticles doped by {Mo₆I₈}⁴⁺ metal clusters

Silica nanoparticles (SNPs) doped by hexanuclear molybdenum cluster complexes [{Mo₆X₈}L₆]n (X = Cl, Br, or I; L = various inorganic or organic ligands) have been recently suggested as materials with a high potential for biomedical applications due to both the outstanding photoluminescent properties and the 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 {Mo₆I₈}⁴⁺ for such applications as bioimaging and photodynamic therapy using human epidermoid larynx carcinoma (Hep-2) cell line as a model. Our results demonstrated both: (i) significant luminescence from cells with internalised molybdenum cluster doped SNPs combined with the low cytotoxicity of particles in the darkness and (ii) significant cytotoxicity of the particles upon photoirradiation. Thus, this research provides strong experimental evidence for high potential of molybdenum cluster doped materials in such biomedical applications as optical bioimaging, biolabeling and photodynamic therapy

A comparative study of hydrophilic phosphine hexanuclear rhenium cluster complexes’ toxicity

Octahedral rhenium cluster compound Na2H8[{Re6Se8}(P(C2H4CONH2)(C2H4COO)2)6] 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 difficulty to control the hydrolysis of initial P(C2H4CN)3 ligand during the reaction process. Therefore, in this report we compare the in vitro and in vivo toxicity of Na2H8[{Re6Se8}(P(C2H4CONH2)(C2H4COO)2)6] with those of related compounds featuring fully hydrolysed form of the phosphine ligand, namely Na2H14[{Re6Q8}(P(C2H4COO)3)6] (Q = S or Se). Our results demonstrate that cytotoxicity and acute in vivo toxicity of the complex Na2H8[{Re6Se8}(P(C2H4CONH2)(C2H4COO)2)6] solutions were considerably lower than those of compounds with fully hydrolysed ligand P(C2H4COOH)3. Such behavior can be explained by the higher osmolality of Na2H14[{Re6Q8}(P(C2H4COO)3)6] versus Na2H8[{Re6Se8}(P(C2H4CONH2)(C2H4COO)2)6]

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 (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6]

Smart emissive hybrid dynamer and nanocomposite made of complementary organic and inorganic emitters combined via a supramolecular Janus synthon

International audienceMonotopic and ditopic blue-emitting anthracene derivatives bearing one or two thymine moieties, respectively, are associated via hydrogen bonds to a red-emitting [Mo6I8(OCOC2F5)(6)](2-) anion, whose charge is counter-balanced by a Janus-type organic synthon made of an imidazolium head bearing an organic chain terminated with a complementary diamidopyridine group. The generated supramolecular hydrogen-bonded complex and dynamers show blue emission in solution and red emission in the solid state. Once embedded in the PMMA film, the dynamer emission colour is controlled by the irradiation time and power in the UV-2A region. This dynamic luminescent behaviour allows for evanescent optical writing on the film

Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties

Neutral Mo3(μ3-S)(μ-S2)3X3(diimine) (X = Cl–, Br–) heteroleptic cluster complexes containing the 1,10-phenanthroline ligands 1H-imidazo[4,5-f][1,10]phenanthroline-2-[3,4-bis(dodecyloxy)phenyl] (IPDOP), 4,7-diphenyl-1,10-phenanthroline (BPhen), and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) were prepared in high yields by straightforward ligand-substitution reactions starting from the [Mo3(μ3-S)(μ-S2)3X6]2– cluster anion. The complexes Mo3S7X4(BPhen) [X = Br– (for 3) and Cl– (for 4)] and Mo3S7X4(tmpphen) [X = Br– (for 5) and Cl– (for 6)] crystallized as tetra-n-butylammonium salts of anionic aggregates (3–6·X)–, in which neutral Mo3S7X3(diiimine)3 cluster molecules participate in non-valence interactions between the axial sulfur atoms, Sax, and a halide anion. The complexes Mo3S7Br4(IPDOP) (1) and Mo3S7Cl4(IPDOP) (2) are luminescent when excited at 330 nm and have maximum emission intensities around 450 nm in DMF and around 435 nm in dichloromethane. The maximum fluorescence quantum yield and the maximum emission lifetime were achieved for complex 2 in DMF(φF = 0.15 and τ = 7.5 ns, respectively). The most important property of complexes 1 and 2 is the shift of their emission spectra in the presence of proton-abstractor anions, such as F–, OH–, and AcO–. When these anions are added to solutions of complexes 1 or 2 in DMF or dichloromethane, the maximum emission wavelength shifts by approximately 90 nm to higher wavelengths