Metal (Au, Pt, Pd, Ni) Bis(dithiolene) complexes as dual-action agents combating cancer and trypanosomatid infections.

Cancer and infection diseases pose severe threats to public health worldwide stressing the need for more effective and efficient treatments. Thus, the search for broad-spectrum activity drugs seems justifiable and urgent. Herein, we investigate the anticancer and antitrypanosomatid (anti-Trypanosoma cruzi) activities of eight monoanionic metal bis(dithiolene) complexes, [PhP][M(R-thiazdt)] with M = Au, Pt, Pd, Ni, containing N-alkyl-1,3-thiazoline-2-thione dithiolene ligands (R-thiazdt) with different alkyl groups (R = Et, tBu).

Mixed-ligand, radical, gold bis(dithiolene) complexes: from single-component conductors to controllable NIR-II absorbers.

Neutral radical bis(dithiolene) gold complexes [Au(dt)]˙ are known to exhibit a strong absorption in the 1400-2000 nm NIR absorption range. Here, we demonstrate that the NIR signature of mixed-ligand bis(dithiolene) gold complexes [Au(dt)(dt)]˙ associating two different dithiolene, dt and dt, is found at higher energy, out of the range of the homoleptic analogs [Au(dt)]˙ and [Au(dt)]˙, in the looked-after NIR-II 1000-1400 nm absorption range. An efficient synthetic approach towards precursor mixed-ligand monoanionic gold bis(dithiolene) complexes [Au(dt)(dt)] is reported.

Structure-activity relationship of anticancer and antiplasmodial gold bis(dithiolene) complexes.

Monoanionic gold bis(dithiolene) complexes were recently shown to display activity against ovarian cancer cells, Gram-positive bacteria, strains and the rodent malaria parasite, . To date, only monoanionic gold(III) bis(dithiolene) complexes with a thiazoline backbone substituted with small alkyl chains have been evaluated for biomedical applications. We now analyzed the influence of the length and the hydrophobicity hydrophilicity of these complexes' alkyl chain on their anticancer and antiplasmodial properties.

Radical and diradical states of bis(molybdenocene dithiolene) complexes.

The synthesis and characterization of two bis(dithiolene) proligands involving heteroatomic linkers such as 1,4-dithiine and dihydro-1,4-disiline between the two protected dithiolene moieties are described. Two bimetallic complexes involving these heteroatomic bridges between two redox active bis(cyclopentadienyl)molybdenum dithiolene moieties have been synthesized and characterized by electrochemistry, spectroelectrochemistry, and their properties rationalized with (TD-)DFT. Cyclic voltammetry experiments show sequential oxidation of the two redox centers with Δ values between successive one-electron transfers varying according to the nature of the bridge.

A Bimetallic Benzene-1,2,4,5-Tetrathiolate (btt) Molybdenocene Complex Cp Mo(btt)MoCp : Radical and Diradical States.

Benzene-1,2,4,5-tetrathiolate (btt) has been used as a bridging ligand to prepare a redox active (molybdenocene dithiolene)-based bimetallic complex Cp Mo(btt)MoCp , which exhibits four successive electron transfers up to the tetracation. Spectro-electrochemical investigations together with DFT and TD-DFT calculations evidence that the two electroactive MoS C metallacycles are electronically coupled in the monocationic as in the dicationic state. Two salts of the dication [Cp Mo(btt)MoCp ] have been structurally characterized with PF and HSO counterions, showing different chair or boat conformations associated with variable folding angles of the two MoS C metallacycles along the S-S hinge.

Broad Spectrum Functional Activity of Structurally Related Monoanionic Au(III) Bis(Dithiolene) Complexes.

The biological properties of sixteen structurally related monoanionic gold (III) bis(dithiolene/ diselenolene) complexes were evaluated. The complexes differ in the nature of the heteroatom connected to the gold atom (AuS for dithiolene, AuSe for diselenolene), the substituent on the nitrogen atom of the thiazoline ring (Me, Et, Pr, iPr and Bu), the nature of the exocyclic atom or group of atoms (O, S, Se, C(CN)) and the counter-ion (PhP or EtN). The anticancer and antimicrobial activities of all the complexes were investigated, while the anti-HIV activity was evaluated only for selected complexes.

Gold(iii) bis(dithiolene) complexes: from molecular conductors to prospective anticancer, antimicrobial and antiplasmodial agents.

The anticancer, antimicrobial and antiplasmodial activities of six gold(iii) bis(dithiolene) complexes were studied. Complexes 1-6 showed relevant anticancer properties against A2780/A2780cisR ovarian cancer cells (IC50 values of 0.08-2 μM), also being able to overcome cisplatin resistance in A2780cisR cells.

Impact of bulky phenylalkyl substituents on the air-stable n-channel transistors of birhodanine analogues.

By introducing bulky 2-phenylethyl groups into sulfur-rich electron acceptors, 5,5'-bithiazolidinylidene-2,2'-dione-4,4'-dithione and 5,5'-bithiazolidinylidene-2,4,2',4'-tetrathione, electron transport with the mobility of 0.27 cm V s with ambient and long-term stability is achieved in thin-film transistors. Bulky groups destroy the intermolecular S-S network, but the long-term transistor stability is maintained.

Hydrogen-bonding interactions in a single-component molecular conductor: a hydroxyethyl-substituted radical gold dithiolene complex.

The anionic hydroxyethyl-substituted gold dithiolene complex [NEt4][Au(EtOH-thiazdt)2] is synthesized and further oxidized to the neutral radical species [Au(EtOH-thiazdt)2](•) through electrocrystallization. Single-crystal X-ray diffraction studies highlight the existence of the two cis and trans isomers for the monoanionic complex, with involvement of the hydroxy group in intermolecular O-H···S hydrogen-bonding interactions. The neutral radical complex, [Au(EtOH-thiazdt)2](•), is isostructural with its known ethyl analogue, namely, [Au(Et-thiazdt)2](•).

A sulfur rich electron acceptor and its [Fe(Cp*)2]+ charge transfer salt with ferromagnetic interactions.

The study of a side product of the aerial dithiolene oxidation allowed the rational and efficient synthesis of a sulfur rich electron acceptor, (E)-3,3'-diethyl-5,5'-bithiazolidinylidene-2,4,2',4'-tetrathione, that presents easily accessible redox states and forms with decamethylferrocene a charge transfer salt exhibiting ferromagnetic coupling.

Variable magnetic interactions between S = 1/2 cation radical salts of functionalizable electron-rich dithiolene and diselenolene Cp2Mo complexes.

A series of Cp(2)Mo(dithiolene) and Cp(2)Mo(diselenolene) complexes containing N-alkyl-1,3-thiazoline-2-thione-4,5-dithiolate ligand (R-thiazdt, R = Me, Et, CH(2)CH(2)OH) and N-alkyl-1,3-thiazoline-2-thione-4,5-diselenolate ligand (R-thiazds, R = Me, Et) have been synthesized. These heteroleptic molybdenum complexes have been characterized by electrochemistry, spectroelectrochemistry, and single crystal X-ray diffraction. They act as very good electron donor complexes with a first oxidation potential 200 mV lower than in the prototypical Cp(2)Mo(dmit) complex and exhibit almost planar MoS(2)C(2) (or MoSe(2)C(2)) metallacycles.

3d4f heterobimetallic dinuclear and tetranuclear complexes involving tetrathiafulvalene as ligands: X-ray structures and magnetic and photophysical investigations.

Six new 3d4f heterobimetallic dinuclear complexes, [(L(1))MLn(hfac)(3)] [M = Cu(II), Ni(II); Ln = Y(III), Er(III), Yb(III); L(1) = 4,5-bis(propylthio)tetrathiafulvalene-N,N'-phenylenebis(salicylideneimine) and hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate], and one tetranuclear complex, [(L(2))Cu(OH)Er(hfac)(3)](2) (where L(2) = 4,5-bis(propylthio)tetrathiafulvalene-N,N'-phenyleneaminosalicylideneimine), have been synthesized. All of the X-ray structures of the coordination complexes have been resolved from single-crystal diffraction. A quantitative magnetic approach has allowed one to determine the Cu-Ln ferromagnetic interaction for Gd(III) (1.

A single molecule magnet behaviour in a D3h symmetry Dy(III) complex involving a quinone-tetrathiafulvalene-quinone bridge.

A Dy(III)-based dinuclear complex was synthesised and characterised by X-ray diffraction on single crystal and magnetic investigations. Dynamic magnetic measurements reveal a single molecule magnet behaviour for 1 which can be described as two single-ion magnets in a D(3h) local symmetry bridged by an acceptor-donor-acceptor ligand.

Ferromagnetic versus antiferromagnetic exchange interactions in tetrathiafulvalene-based 3d/4f heterobimetallic complexes.

(TTF-salphen)M compounds (TTF-salphen(2-)=4,5-bis(propylthio)tetrathiafulvalene-N,N'-phenylenebis(salicylideneimine) dianion; M=Cu(II) and Ni(II)) have been treated with Ln(hfac)(3)·2H(2)O precursors (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion; Ln=Gd(III), Tb(III), and Dy(III)) to elaborate unprecedented 3d/4f TTF-based heterobimetallic complexes of formula [(TTF-salphen)MLn(hfac)(3)]. All the structures of these compounds have been resolved by X-ray diffraction on single crystals. The structures of these complexes are formed by a TTF-salphen(2-) ligand coordinated to the 3d metal ions in the inert tetradentate N(2)O(2) site.

Single-molecule magnet behaviour in a tetrathiafulvalene-based electroactive antiferromagnetically coupled dinuclear dysprosium(III) complex.

The reactions between the [Ln(tta)(3)]·2H(2)O precursors (tta(-)=2-thenoyltrifluoroacetonate anion) and the tetrathiafulvalene-3-pyridine-N-oxide ligands (L(1)) lead to dinuclear complexes of formula [{Ln(tta)(3)(L(1))}(2)]·xCH(2)Cl(2) (x=0.5 for Ln=Dy(III) (1) and x=0 for Ln=Gd(III) (2)). The crystal structure reveals that two {Ln(tta)(3)} moieties are bridged by two donors through the nitroxide groups.

Tetrathiafulvalene-amido-2-pyridine-N-oxide as efficient charge-transfer antenna ligand for the sensitization of Yb(III) luminescence in a series of lanthanide paramagnetic coordination complexes.

The tetrathiafulvalene-amido-2-pyridine-N-oxide (L) ligand has been employed to coordinate 4f elements. The architecture of the complexes mainly depends on the ionic radii of the lanthanides. Thus, the reaction of L in the same experimental protocol leads to three different molecular structure series.

Binuclear Cu(ii) coordination complex involving Cis-tetrathiafulvalene-bis-amido-2-pyridine-N-oxide as bi-anionic ligand: a robust molecular precursor toward magnetic conducting materials.

Synthesis, electrochemical, X-Ray structure, experimental and TD-DFT calculations of photophysical properties have been explored for the [Cu(2)(Cis-TTF-bis-CON-2-Py-N-oxide)(2)] binuclear coordination complex involving Cis-tetrathiafulvalene-bis-amido-2-pyridine-N-oxide as a bi-anionic ligand.

Red-NIR luminescent hybrid poly(methyl methacrylate) containing covalently linked octahedral rhenium metallic clusters.

The embedding of functional inorganic entities into polymer matrices has become an intense field of investigation in which the main challenges are to keep the added value of the inorganic entities while preventing their self-aggregation within the organic matrix. We present a simple way to obtain a homogeneous highly red-NIR luminescent hybrid copolymer that contains covalently bonded nanometric-sized {Re(6)} octahedral clusters. The [Re(6)Se(i)(8)(OH)(a)(6)](4-) cluster complexes are primarily functionalized in two steps with tert-butylpyridine (TBP) and methacrylic acid (MAC) to give neutral [Re(6)Se(8)(TBP)(4)(MAC)(2)] building blocks that are copolymerized with methyl methacrylate (MMA) either in solution or in bulk in the presence of azobisisobutyronitrile as an initiator.

Experimental and theoretical studies on photophysical properties: tuning redox-active amido-tetrathiafulvalene derivatives in paramagnetic coordination complexes.

Amido-5-pyrimidine (1), -4-pyridine (2), -2-pyrazine (3), -2-pyridine (4), and -2-pyridine-N-oxide (5) derivatives of TTF (TTF = tetrathiafulvalene) have been synthesized and characterized. The crystal structure of 1 has been resolved. Their capacities to coordinate paramagnetic transition metal have been explored.

4-(2-Tetrathiafulvalenyl-ethenyl)pyridine (TTF-CH=CH-Py) radical cation salts containing poly(beta-diketonate) rare earth complexes: synthesis, crystal structure, photoluminescent and magnetic properties.

The reactions between the redox-active 4-(2-tetrathiafulvalenyl-ethenyl)pyridine ligand (TTF-CH=CH-Py) and the tris(1,1,1,5,5,5-hexafluoroacetylacetonate)Ln(III) (Ln = La and Nd) lead to the formation of compounds with the formulas {[La(hfac)(5)][(TTF-CH=CH-Py(*+))](2)} (1), {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2) (2), and {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2)(H(2)O)(C(6)H(14))(0.5) (3) (hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion). These compounds have been characterized by single-crystal X-ray diffraction, optical, and magnetic measurements.

Binuclear gadolinium(III) coordination complex based on bridging tetrathiafulvalenecarboxylate radical cations.

X-Ray structure, photophysical and magnetic properties have been explored for the binuclear gadolinium(III) coordination complex based on bridging tetrathiafulvalenecarboxylate radical cations [Gd(hfac)(3)(micro-TTF (+)COO(-))](2).

2D and 3D Polymeric Wells-Dawson polyoxometelates: synthesis, crystal structures, and cyclic voltammetry of [(M(H(2)O)(4))(x)][H(6-2x)P(2)W(18-n)Mo(n)O(62)] (M = Cu(II), Co(II), Ni(II)).

The synthesis, X-ray crystal structures, cyclic voltammetry, and IR and (31)P NMR characterizations of five new Wells-Dawson-type polyoxometalates are reported, the formulas of which being [(Cu(H(2)O)(4))(2.5)][HP(2)W(18)O(62)].11.