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 ΔE values between successive one-electron transfers varying according to the nature of the bridge. Depending on the nature of the heteroatomic bridge, the bis-oxidized complexes exhibit either a diradical character with both radicals essentially localized on the metallacycles, or a closed-shell dicationic state.

Block Copolymer Micelles Encapsulating Au(III) Bis(Dithiolene) Complexes as Promising Nanostructures with Antiplasmodial Activity.

Block copolymer micelles (BCMs) can be used to improve the solubility of lipophilic drugs and increase their circulation half-life. Hence, BCMs assembled from MePEG-b-PCL were evaluated as drug delivery systems of gold(III) bis(dithiolene) complexes (herein AuS and AuSe) to be employed as antiplasmodial drugs. These complexes exhibited remarkable antiplasmodial activity against liver stages of the Plasmodiumberghei parasite, and low toxicity in a model of zebrafish embryos. To improve the complexes' solubility, BCMs were loaded with AuS, AuSe, and the reference drug primaquine (PQ). PQ-BCMs (Dh = 50.9 ± 2.8 nm), AuSe-BCMs (Dh = 87.1 ± 9.7 nm), and AuS-BCMs (Dh = 72.8 ± 3.1 nm) were obtained with a loading efficiency of 82.5%, 55.5%, and 77.4%, respectively. HPLC analysis and UV-Vis spectrophotometry showed that the compounds did not suffer degradation after encapsulation in BCMs. In vitro release studies suggest that AuS/AuSe-BCMs present a more controlled release compared with PQ-loaded BCMs. The antiplasmodial hepatic activity of the drugs was assessed in vitro and results indicate that both complexes present higher inhibitory activity than PQ, although encapsulated AuS and AuSe presented lower activity than their non-encapsulated counterparts. Nevertheless, these results suggest that the use of BCMs as delivery vehicles for lipophilic metallodrugs, particularly AuS and AuSe, could enable the controlled release of complexes and improve their biocompatibility, constituting a promising alternative to conventional antimalarial treatments.

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)2) and the counter-ion (Ph4P+ or Et4N+). The anticancer and antimicrobial activities of all the complexes were investigated, while the anti-HIV activity was evaluated only for selected complexes. Most complexes showed relevant anticancer activities against Cisplatin-sensitive and Cisplatin-resistant ovarian cancer cells A2780 and OVCAR8, respectively. After 48 h of incubation, the IC50 values ranged from 0.1-8 µM (A2780) and 0.8-29 µM (OVCAR8). The complexes with the Ph4P+ ([P]) counter-ion are in general more active than their Et4N+ ([N]) analogues, presenting IC50 values in the same order of magnitude or even lower than Auranofin. Studies in the zebrafish embryo model further showed that, despite their marked anticancer effect, the complexes with [P] counter-ion exhibited low in vivo toxicity. In general, the exocyclic exchange of sulfur by oxygen or ylidenemalononitrile (C(CN)2) enhanced the compounds toxicity. Most complexes containing the [P] counter ion exhibited exceptional antiplasmodial activity against the Plasmodium berghei parasite liver stages, with submicromolar IC50 values ranging from 400-700 nM. In contrast, antibacterial/fungi activities were highest for most complexes with the [N] counter-ion. Auranofin and two selected complexes [P][AuSBu(=S)] and [P][AuSEt(=S)] did not present anti-HIV activity in TZM-bl cells. Mechanistic studies for selected complexes support the idea that thioredoxin reductase, but not DNA, is a possible target for some of these complexes. The complexes [P] [AuSBu(=S)], [P] [AuSEt(=S)], [P] [AuSEt(=Se)] and [P] [AuSeiPr(=S)] displayed a strong quenching of the fluorescence intensity of human serum albumin (HSA), which indicates a strong interaction with this protein. Overall, the results highlight the promising biological activities of these complexes, warranting their further evaluation as future drug candidates with clinical applicability.

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. Complex 1 also exhibited significant antimicrobial activity against Staphylococcus aureus (minimum inhibitory concentration (MIC) values of 12.1 ± 3.9 µg mL-1) and both Candida glabrata and Candida albicans (MICs of 9.7 ± 2.7 and 19.9 ± 2.4 µg mL-1, respectively). In addition, all complexes displayed antiplasmodial activity against the Plasmodium berghei parasite liver stages, even exhibiting better results than the ones obtained using primaquine, an anti-malarial drug. Mechanistic studies support the idea that thioredoxin reductase, but not DNA, is a possible target of these complexes. Complex 1 is stable under biological conditions, which would be important if this compound is ever to be considered as a drug. Overall, the results obtained evidenced the promising biological activity of complex 1, which might have potential as a novel anticancer, antimicrobial and antiplasmodial agent to be used as an alternative to current therapeutics.

Stable Metallic State of a Neutral-Radical Single-Component Conductor at Ambient Pressure.

Molecular metals have been essentially obtained with tetrathiafulvalene (TTF)-based precursors, either with multicomponent ionic materials or, in a few instances, with single-component systems. In that respect, gold bis(dithiolene) complexes, in their neutral radical state, provide a prototype platform toward such single-component conductors. Herein we report the first single-component molecular metal under ambient pressure derived from such Au complexes without any TTF backbone. This complex exhibits a conductivity of 750 S·cm-1 at 300 K up to 3800 S·cm-1 at 4 K. First-principles electronic structure calculations show that the striking stability of the metallic state finds its origin in sizable internal electron transfer from the SOMO-1 to the SOMO of the complex as well as in substantial interstack and interlayer interactions.

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 cm2 V-1 s-1 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. Here, benzyl groups realize one-dimensional stacking structures, whereas 2-phenylethyl groups lead to herringbone structures.

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](•). It exhibits a semiconducting behavior (σRT = 0.05-0.07 S cm(-1)) at room temperature and ambient pressure with an activation energy of 0.14 eV. Comparison of the crystal structures and transport and magnetic properties with those of the prototypical [Au(Et-thiazdt)2](•) single-component conductor shows that the replacement of ethyl by a slightly bulkier hydroxyethyl substituent affects only weakly the overlap interactions, complemented here by added O-H···S hydrogen-bonding interactions.

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. All five complexes formed charge transfer salts with a weak (TCNQ) and a strong acceptor (TCNQF(4)), affording ten different charge-transfer salts, all with 1:1 stoichiometry. Crystal structure determinations show that the S/Se substitution in the metallacycle systematically affords isostructural salts, while the Cp(2)Mo(R-thiazdt) complexes with R equals ethyl or CH(2)CH(2)OH can adopt different structures, depending on the involvement of the hydroxyl group into intra- or intermolecular hydrogen bonding interactions. Magnetic susceptibility data of the salts are correlated with their structural organization, demonstrating that a face-to-face organization of the Me-thiazdt (or Me-thiazds) ligand favors a strong antiferromagnetic interaction, while the bulkier R = Et or R = CH(2)CH(2)OH substituents can completely suppress such intermolecular interactions, with the added contribution of hydrogen bonding to the solid state organization.

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) (1.29 cm(-1)) and Tb(III) (0.40 cm(-1)) and the antiferromagnetic interaction for Dy(III) (-0.46 cm(-1)) and Yb(III) (-2.25 cm(-1)), while in the case of Er(III), the magnetic interactions are negligible. The UV-visible absorption properties have been studied in a chloroform solution and rationalized by DFT and TD-DFT calculations. Upon oxidation, intramolecular SOMO → LUMO (20,800 cm(-1)) and SOMO-n → SOMO (11,350 cm(-1)) charge transfers appear, while the HOMO → LUMO charge transfers (20,750 cm(-1)) disappear. The reversibility of the oxidation has been confirmed by electrochemistry and absorption properties upon the addition of a reducing agent. Irradiation at the HOMO → LUMO charge-transfer energy of the dinuclear complex [(L(1))NiY(hfac)(3)] induces a ligand-centered fluorescence at 14,450 cm(-1).

In solution sensitization of Er(III) luminescence by the 4-tetrathiafulvalene-2,6-pyridinedicarboxylic acid dimethyl antenna ligand.

In the [Er(hfac)(3)(L)](2) complex (1) (L = 4-tetrathiafulvalene-2,6-pyridinecarboxylic acid dimethyl ester), the Er(III) ion is bonded to the tridentate coordination site. Electrochemical and photophysical measurements in solution reveal that the tetrathiafulvalene moiety is a versatile antenna for erbium luminescence sensitization at 6540 cm(-1) upon excitation in the low-energy charge transfer transition (donor to acceptor charge transfer) at 16600 cm(-1) assigned via time-dependent density functional theory calculations.

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. The Ln(hfac)(3) fragment is coordinated to the (TTF-salphen)M one through the two phenolate bridges. Even if the complexes are similar in both Cu(II) and Ni(II) families, the crystal packing is different. In the first case, dimers of TTF-salphen(2-) donors constitute the organic network. In the other case, a reminiscent organic network is observed with S···S contacts. The photophysical properties of [(TTF-salphen)CuDy(hfac)(3)] (3) in chloroform solution highlight the redshift of the TTF→salphen charge transfer (400 cm(-1)) relative to the analogue excitations in (TTF-salphen)Cu, which attest to the stability of these structures in solution. Static magnetic measurements have allowed us to quantify the ferromagnetic interactions (J=+1.29 cm(-1)) between Cu(II) and Gd(III) in the [(TTF-salphen)CuGd(hfac)(3)] complex. Finally, an empirical method that consists of the comparisons of the magnetic properties of [(TTF-salphen)CuTb(hfac)(3)] with [(TTF-salphen)NiTb(hfac)(3)] and [(TTF-salphen)CuDy(hfac)(3)] with [(TTF-salphen)NiDy(hfac)(3)] has established that ferromagnetic interactions take place between Cu(II) and Tb(III) ions, whereas unusual antiferromagnetic interactions have been identified between Cu(II) and Dy(III) ions.

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. The Dy(III) centre adopts a distorted square antiprismatic oxygenated polyhedron structure. The antiferromagnetic nature of the exchange interaction between the two Dy(III) ions has been determined by two methods: 1) an empirical method using the [Dy(hfac)(3)(L(2))(2)] mononuclear complex as a model (3) (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, L(2)=tetrathiafulvaleneamido-2-pyridine-N-oxide ligand), and 2) assuming an Ising model for the Dy(III) ion giving an exchange energy of -2.30 cm(-1), g=19.2 in the temperature range of 2-10 K. The antiferromagnetic interactions have been confirmed by a quantitative determination of J for the isotropic Gd(III) derivative (J=-0.031 cm(-1), g=2.003). Compound 1 displays a slow magnetisation relaxation without applied external magnetic fields. Alternating current susceptibility shows a thermally activated behaviour with pre-exponential factors of 5.48(4)×10(-7) s and an energy barrier of 87(1) K. The application of an external field of 1.6 kOe compensates the antiferromagnetic interactions and opens a new quantum tunnelling path.

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 [Ln(2)(hfac)(5)(O(2)CPhCl)(L)(3)]·2 H(2)O (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, O(2)CPhCl(-)=3-chlorobenzoate anion) and mononuclear [Ln(hfac)(3)(L)(2)] complexes were obtained by using rare-earth ions with either large (Ln(III)=Pr, Gd) or small (Ln(III)=Y, Yb) ionic radius, respectively, whereas the use of Tb(III) that possesses an intermediate ionic radius led to the formation of a binuclear complex of formula [Tb(2)(hfac)(4)(O(2)CPhCl)(2)(L)(2)]. Antiferromagnetic interactions have been observed in the three dinuclear compounds by using an extended empirical method. Photophysical properties of the coordination complexes have been studied by solid-state absorption spectroscopy, whereas time-dependent density functional theory (TD-DFT) calculations have been carried out on the diamagnetic Y(III) derivative to build a molecular orbital diagram and to reproduce the absorption spectrum. For the [Yb(hfac)(3)(L)(2)] complex, the excitation at 19,600 cm(-1) of the HOMO→LUMO+1/LUMO+2 charge-transfer transition induces both line-shape emissions in the near-IR spectral range assigned to the (2)F(5/2)→(2)F(7/2) (9860 cm(-1)) ytterbium-centered transition and a residual charge-transfer emission around 13,150 cm(-1). An efficient antenna effect that proceeds through energy transfer from the singlet excited state of the tetrathiafulvalene-amido-2-pyridine-N-oxide chromophore is evidence of the Yb(III) sensitization.

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. Several samples containing 0, 0.025, 0.05, and 0.1 wt % of functionalized {Re(6)} clusters were prepared. As the {Re(6)} cluster/MMA ratio is very low, the obtained copolymers keep the entire processability of pure poly(methyl methacrylate) (PMMA), as demonstrated by differential scanning calorimetry and thermogravimetric analysis. Voltammetric and luminescence studies also indicate that the intrinsic properties of the clusters are preserved within the polymer matrix. All the samples show a bright (emission quantum yield=0.07), broad, and structureless emission band, which extends from lambda=600 nm to more than lambda=950 nm, with the maximum wavelength centered around lambda(em)=710 nm either in solution or in the solid state. Moreover, the high stability of the incorporated inorganic phosphors prevents the material from photobleaching, and thus the luminescence properties are kept entirely even after nine months of ageing.

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. The following new molecular compounds have been synthesized and obtained as single crystals: {[Cu(hfac)(2)(1)](H(2)O)}(2) (6), cis-[Mn(hfac)(2)(2)(2)](THF)(2) (7), trans-[Cu(hfac)(2)(3)(2)] (8), trans-[Cu(hfac)(2)(4)(2)] (9), and trans-[M(hfac)(2)(5)(2)] (M = Cu (10), Mn (11), Zn (12)). The crystal structures reveal that the nature of the coordinating substituent plays a fundamental role on the crystalline organization. Cyclic voltammetry measurements have been performed for all the species and they have permitted us to observe the redox activity of the free and linked donors. EPR measurements are in agreement with the solid-state structures. All the ligands and corresponding coordination complexes have been studied by UV-visible absorption spectroscopy. Gaussian deconvolutions have been performed to fit the experimental solid-state absorption curves. Molecular orbital diagram for ligands 4 and 5; and their coordination complexes have been determined. The nature of the thirty to fifty low-lying monoelectronic transitions occurring in the TTF derivatives have been identified by TD-DFT calculations and their corresponding UV-visible absorption spectra have been simulated. Concerning the open-shell complexes, the excitations in the low energy region of their spectra have been calculated to determine the coordination effect on the TTF to acceptor transitions of the ligand fragments.

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. Compounds 1, 2, and 3 crystallize in the monoclinic C2/c, triclinic P1, and monoclinic P2(1)/c space groups, respectively. La(III) adopts a tetradecahedral geometry, while Nd(III) stands in a distorted capped square antiprism one. In 1, the inorganic network is formed by the [La(hfac)(5)](2-) dianionic complexes, while it is formed by a pseudo-dimeric dianionic unit of formula {[Nd(hfac)(4)(H(2)O)](2)}(2-) in 2 and 3. In all crystal structures, the organic network is constituted by the TTF-CH=CH-Py(*+) radical cations. The inorganic and organic networks interact through intermolecular contacts between the pyridine moieties of the TTF-CH=CH-Py(*+) radical cations and the Ln(III) ions. The luminescence properties of the Nd(III) ions (9400 cm(-1)) and fluorescence band of the TTF-CH=CH-Py(*+) radical cations (10200 cm(-1)) have been observed and studied for compound 2. Complexes 2 and 3 are paramagnetic because of Nd(III) ions. Compound 2 is a paramagnetic luminescent TTF-radical-cation-based material. Resistivity measurements have also been performed on these materials.

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)].11.33H(2)O (4), [(Cu(H(2)O)(4))(2.4)][H(1.2)P(2)W(12)Mo(6)O(62)].11.4H(2)O (5), [(Cu(H(2)O)(4))(2.3)][H(1.4)P(2)W(15)Mo(3)O(62)].10.1H(2)O (6), [Co(H(2)O)(4))(2.3)][H(1.4)P(2)W(14)Mo(4)O(62)].18.8H(2)O (7), and [Ni(H(2)O)(4))(1.85)][H(2.3)P(2)W(15)Mo(3)O(62)].20.6H(2)O (8). These compounds are obtained as crystalline materials from the corresponding acids by substitution of a transition metal in aqueous solution. Compounds 4, 5, and 6 are isostructural; their crystal structure consists of 2D polymeric hexagonal layers where each Wells-Dawson anion is connected to six neighbors by [CuO(6)] octahedra. On the other hand, compounds 7 and 8, which are also isostructural, present a 3D structure where the Mo-substituted [P(2)W(14)Mo(4)O(62)] units are connected by [MO(6)] octahedra (M = Co(II), Ni(II)). Different types of substitution modes of Mo ions are observed within polyanions. Cyclic voltammetry shows that Cu(II) derivatives have similar behavior but different from that of the starting compounds. No electrochemical activity has been detected for the Ni-containing compound 8.