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The quenching of the near infrared light emission in Er(super 3+) complexes induced by the resonant dipolar interaction between the rare-earth ion and high frequency vibrations of the organic ligand is investigated. The model accounts well for the available experimental results in Er(super 3+) complexes, and predicts an ~ 100% light emission quantum yield in fully halogenated systems.

The synthesis, structure, and physical properties of BIS(ethylenedithio)tetrathiafulvalene Ni(1,2,5-thiadiazole-3,4-dihiolate)2 [(BEDT-TTF)[Ni(tdas)2], which is the first example of a salt containing monomeric [Ni(tdas)2](super -) monoanions, are reported. It can be concluded that the unpaired electron lies on the [Ni(tdas)2](super -) anions.

The synthesis, X-ray structure, magnetic and transport properties of the compound Ni(dmf)6[Ni(dsit)2]2 (dmf=dimethylformamide, dsit=1,3-dithiole-2-thione-4,5-diselenolate) are described. This compound crystallizes in the monoclinic space group P21/c, with a=18.709(6), b=22.975(5), c=20.418(5) A˚, β=99.31(2)° and Z=6; its structure consists of [Ni(dsit)2]22− dimers and isolated [Ni(dmf)6]2+ cations both centrosymmetric and non-centrosymmetric. The dimers are packed forming chains along the [101] direction with short Se·Se interdimer contacts. Additional interchains S·S contacts render this structure a three-dimensional character, never observed so far in other [Ni(dsit)2]− salts. This compound exhibits semiconducting behavior with a room temperature conductivity (1 S cm−1) much higher than those reported for other salts of the [Ni(dsit)2]− anion. Tight-binding band structure calculations were used to analyze the origin of the semiconducting properties of this salt. The magnetic susceptibility shows Curie behavior with C=1.25 emu K mol−1, typical of isolated Ni(II) ions as expected for the octahedrally coordinated [Ni(dmf)6]2+ cations. [Copyright &y& Elsevier]

A seventh blind test of crystal structure prediction was organized by the Cambridge Crystallographic Data Centre featuring seven target systems of varying complexity: a silicon and iodine-containing molecule, a copper coordination complex, a near-rigid molecule, a cocrystal, a polymorphic small agrochemical, a highly flexible polymorphic drug candidate, and a polymorphic morpholine salt. In this first of two parts focusing on structure generation methods, many crystal structure prediction (CSP) methods performed well for the small but flexible agrochemical compound, successfully reproducing the experimentally observed crystal structures, while few groups were successful for the systems of higher complexity. A powder X-ray diffraction (PXRD) assisted exercise demonstrated the use of CSP in successfully determining a crystal structure from a low-quality PXRD pattern. The use of CSP in the prediction of likely cocrystal stoichiometry was also explored, demonstrating multiple possible approaches. Crystallographic disorder emerged as an important theme throughout the test as both a challenge for analysis and a major achievement where two groups blindly predicted the existence of disorder for the first time. Additionally, large-scale comparisons of the sets of predicted crystal structures also showed that some methods yield sets that largely contain the same crystal structures., (open access.)

The potential of aerogels as catalysts for the synthesis of a relevant class of bis-heterocyclic compounds such as bis(indolyl)methanes was investigated. In particular, the studied catalyst was a nanocomposite aerogel based on nanocrystalline nickel ferrite (NiFe 2 O 4 ) dispersed on amorphous porous silica aerogel obtained by two-step sol-gel synthesis followed by gel drying under supercritical conditions and calcination treatments. It was found that the NiFe 2 O 4 /SiO 2 aerogel is an active catalyst for the selected reaction, enabling high conversions at room temperature, and it proved to be active for three repeated runs. The catalytic activity can be ascribed to both the textural and acidic features of the silica matrix and of the nanocrystalline ferrite. In addition, ferrite nanocrystals provide functionality for magnetic recovery of the catalyst from the crude mixture, enabling time-effective separation from the reaction environment. Evidence of the retention of species involved in the reaction into the catalyst is also pointed out, likely due to the porosity of the aerogel together with the affinity of some species towards the silica matrix. Our work contributes to the study of aerogels as catalysts for organic reactions by demonstrating their potential as well as limitations for the room-temperature synthesis of bis(indolyl)methanes.

Nanoporous (NP) gold, the most extensively studied and efficient NP metal, possesses exceptional properties that make it highly attractive for advanced technological applications. Notably, its remarkable catalytic properties in various significant reactions hold enormous potential. However, the exploration of its catalytic activity in the degradation of water pollutants remains limited. Nevertheless, previous research has reported the catalytic activity of NP Au in the degradation of methyl orange (MO), a toxic azo dye commonly found in water. This study aims to investigate the behavior of nanoporous gold in MO solutions using UV-Vis absorption spectroscopy and high-performance liquid chromatography. The NP Au was prepared by chemical removal of silver atoms of an AuAg precursor alloy prepared by ball milling. Immersion tests were conducted on both pellets and powders of NP Au, followed by examination of the residual solutions. Additionally, X-ray photoelectron spectroscopy and electrochemical impedance measurements were employed to analyze NP Au after the tests. The findings reveal that the predominant and faster process involves the partially reversible adsorption of MO onto NP Au, while the catalytic degradation of the dye plays a secondary and slower role in this system.

The fight against climate change has delineated new objectives, among which one of the most crucial is the replacement of high-energy-intensity materials in the construction sector with more sustainable and thermally efficient alternatives to reduce indirect emissions. Consequently, the thermal properties of materials assume fundamental importance. In this regard, the large-scale use of earth represents a promising option, not only due to its widespread availability but especially for its minimal embodied energy. However, to enhance its durability, it is necessary to stabilize the mixtures of raw materials. This study analyzes experimental systems based on earth stabilized with bio-based polymers to evaluate their thermal properties and how these vary depending on the selected mix-design. The experimental measurements showed thermal properties comparable to conventional materials. As expected, thermal conductivity increases when porosity decreases. The minimum value is equal to 0.216 W/m·K vs. a porosity of 43.5%, while the maximum is 0.507 W/m·K vs. a porosity of 33.2%. However, the data obtained for individual systems may vary depending on the topological characteristics, which were analyzed through a model for granular materials. The modeling suggests correlations between microstructures and thermal behaviour, which can be useful to develop tools for the mix-design procedure.

We have synthesized a co-condensed hollow ethane-bipyridine periodic mesoporous organosilica (HEt-bpy-PMO) as a host material to anchor lanthanides for the purpose of developing a multifunctional chemical sensor. The host material was grafted with lanthanide chloride salts or complexes. The luminescence properties of the developed series of hybrid materials were studied in detail in the solid-state and after dispersing in water. The Eu 3+ or Tb 3+ singly incorporated materials were investigated for their use as ion sensors, showing ions selectivity towards Cu 2+ , Co 2+ and Fe 3+ . Additionally, the Eu 3+ or Tb 3+ incorporated materials showed obvious luminescence quenching behavior towards acetone compared to other organic solvents, indicating excellent acetone sensing selectivity.

The use of tailored medication delivery in cancer treatment has the potential to increase efficacy while decreasing unfavourable side effects. For researchers looking to improve clinical outcomes, chemotherapy for cancer continues to be the most challenging topic. Cancer is one of the worst illnesses despite the limits of current cancer therapies. New anticancer medications are therefore required to treat cancer. Nanotechnology has revolutionized medical research with new and improved materials for biomedical applications, with a particular focus on therapy and diagnostics. In cancer research, the application of metal nanoparticles as substitute chemotherapy drugs is growing. Metals exhibit inherent or surface-induced anticancer properties, making metallic nanoparticles extremely useful. The development of metal nanoparticles is proceeding rapidly and in many directions, offering alternative therapeutic strategies and improving outcomes for many cancer treatments. This review aimed to present the most commonly used nanoparticles for cancer applications.

The self-assembly reaction of the neutral dicyano-bis(1,10-phenanthroline) iron(II) complex with lanthanide ions (Ln = Eu(III), Gd(III), Er(III)) provided two different classes of heterometallic cyano-bridged 3 d -4 f architectures depending on the nature of the counteranion, irrespective of the size of the 4 f metal ion. Tetranuclear oligomers with a squared Fe 2 Ln 2 core were isolated when using nitrate salts, whereas unusual 1D polymeric chains were obtained when resorting to triflate salts under the same synthetic conditions. It is shown that the different structural motifs have a remarkable impact on the thermal stability and the optical properties of the compounds, which display a notable optical ipsochromism of the parent Fe(II) complex upon coordination with the Ln ion. This effect is significantly more pronounced in the polymeric chain than in the Fe 2 Ln 2 oligomer both in solution and in the solid state. Structural evidence suggests that this behavior is likely related to the geometry of the CN-Ln bridge. On the other hand, more extended π-stacking interactions in the oligomer give rise to a broad charge-transfer absorption (600-1500 nm), making this compound promising as NIR absorber. Density Functional Theory calculations and electrochemical studies demonstrate that the observed negative chromism originates from the stabilization of a mixed metal/cyanide character HOMO with respect to a phenanthroline-centered LUMO.

The packing interactions of a series of electron donor (D) and electron acceptor (A) charge transfer (CT) near-IR absorbers based on platinum-dithiolene complexes are reinvestigated here as a case study also by using the Hirshfeld surface analysis. This analysis on systems, which exhibit the 1:1, 2:1 and 2:2 columnar stacking patterns between D and A, allows us to point out that several interactions of atoms and fragments are involved in the stacking interactions but also that only a limited fraction of these interactions, limited to the 1:1 D/A columnar stacking case, can be relatable to the absorption features of this class of compounds.

The cobalt complex ( I ) with cyclopentadienyl and 2-aminothiophenolate ligands was investigated as a homogeneous catalyst for electrochemical CO 2 reduction. By comparing its behavior with an analogous complex with the phenylenediamine ( II ), the effect of sulfur atom as a substituent has been evaluated. As a result, a positive shift of the reduction potential and the reversibility of the corresponding redox process have been observed, also suggesting a higher stability of the compound with sulfur. Under anhydrous conditions, complex I showed a higher current enhancement in the presence of CO 2 (9.41) in comparison with II (4.12). Moreover, the presence of only one -NH group in I explained the difference in the observed increases on the catalytic activity toward CO 2 due to the presence of water, with current enhancements of 22.73 and 24.40 for I and II , respectively. DFT calculations confirmed the effect of sulfur on the lowering of the energy of the frontier orbitals of I , highlighted by electrochemical measurements. Furthermore, the condensed Fukui function f - values agreed very well with the current enhancement observed in the absence of water.

The present case study reports a shear rheological characterization in the temperature domain of inks and pastes loaded with conductive High Reactivity Carbonaceous Material (HRCM) consisting mainly of few-layers graphene sheets. The combined effect of filler concentration and applied shear rate is investigated in terms of the shear viscosity response as a function of testing temperature. The non-Newtonian features of shear flow ramps at constant temperature are reported to depend on both the HRCM load and the testing temperature. Moreover, temperature ramps at a constant shear rate reveal a different viscosity-temperature dependence from what is observed in shear flow ramps while maintaining the same filler concentration. An apparent departure from the well-known Vogel-Fulcher-Tamman relationship as a function of the applied shear rate is also reported.

A series of 6- and 6,8-halocoumarin derivatives have been investigated as potential antiproliferative compounds against a panel of tumor and normal cell lines. Cytotoxic effects were determined by the MTT method. To investigate the potential molecular mechanism involved in the cytotoxic effect, apoptosis assay, cell cycle analysis, reactive oxygen species (ROS), and reduced glutathione analysis were performed. Among the screened compounds, coumarins 6,8-dibromo-2-oxo-2 H -chromene-3-carbonitrile 2h and 6,8-diiodo-2-oxo-2 H -chromene-3-carbonitrile 2k exhibited the most antiproliferative effect in thyroid cancer-derived cells TPC-1. The apoptosis assay showed that both 2h and 2k induced apoptosis in TPC-1 thyroid cancer cells. According to these experiments, both coumarins induced a slight increase in TPC-1 cells in the G2/M phase and a decrease in the S phase. A significant increase in ROS levels was observed in TPC-1 treated with diiodocoumarin 2k , while the dibromocoumarin 2h induced a decrease in ROS in a dose and time-dependent manner.

Nanoporous (NP) metals represent a unique class of materials with promising properties for a wide set of applications in advanced technology, from catalysis and sensing to lightweight structural materials. However, they typically suffer from low thermal stability, which results in a coarsening behavior not yet fully understood. In this work, we focused precisely on the coarsening process undergone by NP Au, starting from the analysis of data available in the literature and addressing specific issues with suitably designed experiments. We observe that annealing more easily induces densification in systems with short characteristic lengths. The NP Au structures obtained by dealloying of mechanically alloyed AuAg precursors exhibit lower thermal stability than several NP Au samples discussed in the literature. Similarly, NP Au samples prepared by annealing the precursor alloy before dealloying display enhanced resistance to coarsening. We suggest that the microstructure of the precursor alloy, and, in particular, the grain size of the metal phases, can significantly affect the thermal stability of the NP metal. Specifically, the smaller the grain size of the parent alloy, the lower the thermal stability., Competing Interests: The authors declare no conflict of interest.

Magnetic scaffolds have been investigated as promising tools for the interstitial hyperthermia treatment of bone cancers, to control local recurrence by enhancing radio- and chemotherapy effectiveness. The potential of magnetic scaffolds motivates the development of production strategies enabling tunability of the resulting magnetic properties. Within this framework, deposition and drop-casting of magnetic nanoparticles on suitable scaffolds offer advantages such as ease of production and high loading, although these approaches are often associated with a non-uniform final spatial distribution of nanoparticles in the biomaterial. The implications and the influences of nanoparticle distribution on the final therapeutic application have not yet been investigated thoroughly. In this work, poly-caprolactone scaffolds are magnetized by loading them with synthetic magnetic nanoparticles through a drop-casting deposition and tuned to obtain different distributions of magnetic nanoparticles in the biomaterial. The physicochemical properties of the magnetic scaffolds are analyzed. The microstructure and the morphological alterations due to the reworked drop-casting process are evaluated and correlated to static magnetic measurements. THz tomography is used as an innovative investigation technique to derive the spatial distribution of nanoparticles. Finally, multiphysics simulations are used to investigate the influence on the loading patterns on the interstitial bone tumor hyperthermia treatment.

In the context of new efficient and safe leaching agents for noble metals, this paper describes the capability of the Me 2 pipdt/I 2 mixture (where Me 2 pipdt = N,N'-dimethyl-piperazine-2,3-dithione) in organic solutions to quantitatively dissolve Au, Pd, and Cu metal powders in mild conditions (room temperature and pressure) and short times (within 1 h in the reported conditions). A focus on the structural insights of the obtained coordination compounds is shown, namely [AuI 2 (Me 2 pipdt)]I 3 ( 1 ), [Pd(Me 2 pipdt) 2 ]I 2 ( 2a ) and [Cu(Me 2 pipdt) 2 ]I 3 ( 3 ), where the metals are found, respectively, in 3+, 2+ and 1+ oxidation states, and of [Cu(Me 2 pipdt) 2 ]BF 4 ( 4 ) and [Cu(Me 2 dazdt) 2 ]I 3 ( 5 ) (Me 2 dazdt = N , N '-dimethyl-perhydrodizepine-2,3-dithione) compared with 3 . Au(III) and Pd(II) ( d 8 configuration) form square-planar complexes, whereas Cu(I) ( d 10 ) forms tetrahedral complexes. Density functional theory calculations performed on the cationic species of 1 - 5 help to highlight the nature of the bonding in the different complexes. Finally, the valorization of the noble metals-rich leachates is assessed. Specifically, gold metal is quantitatively recovered from the solution besides the ligands, showing the potential of these systems to promote metal recycling processes.

A comprehensive investigation of the functional properties of heteroleptic donor-M-acceptor dithiolene complexes Bu 4 N[M II (L1)(L2)] is presented (M = Pd, Pt). The acceptor L1 consists of the chiral ( R )-(+)α-methylbenzyldithiooxamidate (( R )-α-MBAdto), the donor L2 is 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit) in 1 (Pd) and 2 (Pt), 1,2-dicarbomethoxyethylenedithiolate (ddmet) in 3 (Pd) and 4 (Pt), or [4',5':5,6][1,4]dithiino[2,3- b ]quinoxaline-1',3'-dithiolato (quinoxdt) in 5 (Pd) and 6 (Pt). L1 is capable of undergoing proton exchange and promoting crystal formation in noncentrosymmetric space groups. L2 has different molecular structures while it maintains similar electron-donating capabilities. Thanks to the synergy of the ligands, 1 - 6 behave as H + and Ag + switchable linear chromophores. Moreover, the compounds exhibit a H + -switchable second-order NLO response in solution, which is maintained in the bulk for 1 , 3 , and 4 when they are embedded into a PMMA poled matrix. 5 and 6 show unique anti-Kasha H + and Ag + tunable colored emission originating from the quinoxdt ligand. A correlation between the electronic structure and properties is shown through density functional theory (DFT) and time-dependent DFT calculations.

We investigated the anti-Kasha photochemistry and anti-Kasha emission of d 8 -metal donor-acceptor dithiolene with femtosecond UV-vis transient absorption spectroscopy and molecular modeling. Experimentally, we found a lifetime of 1.4 ps for higher excited states, which is exceptionally long when compared to typical values for internal conversion (IC) (10 s of fs or less). Consequently, a substantial emission originates from the second excited state. Molecular modeling suggests this to be a consequence of the spatially separated molecular orbitals of the first and second excited states, which gives a charge transfer character to the IC. More surprisingly, we found that the inherent flexibility of the molecule allows the metal complex to access different configurations depending on the photoexcited state. We believe that this unique manifestation of anti-Kasha photoinduced conformational isomerization is facilitated by the exceptionally long lifetime of the second excited state.

The preparation and characterization of Ni(II) ( 1F ) and Cu(II) ( 2F ) complexes of the ligand 15,16,17,18,19,20,21,22-octafluoro-dibenzotetraaza[14]annulene (L F ) are here reported. These compounds have been characterized by elemental analysis, mass and UV-vis spectroscopies, single-crystal X-ray diffraction, and computational studies. The effects due to the presence of fluorine atoms have been highlighted by comparison with the analogous complexes of the ligand L H (Ni: 1H ; Cu: 2H ), which bears hydrogen atoms at the benzenoid rings instead of fluorine. 1F and 2F are isostructural, with the metal ions bound to the four nitrogen atoms in a square-planar geometry and where the planar molecules are arranged in a herringbone motif in the crystal lattice. Remarkable differences in the intermolecular interactions between 1F and 2F and the corresponding H-complexes are shown by Hirshfeld surface calculations. Moreover, the effects of fluorination on the electronic structures have been investigated by density functional theory (DFT) and time-dependent DFT calculations. The compounds with L F and L H ligands present corresponding molecular orbitals (MOs) with similar shapes. Furthermore, while the presence of F-atoms lowers the energy of the MOs in comparison with those of the L H complexes, it does not remarkably affect the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) and HOMO-LUMO + 1 gaps, in agreement with the UV-vis results., Competing Interests: The authors declare no competing financial interest.

Complex [Pt(iPr 2 pipdt)(Quinoxdt)] (iPr 2 pipdt=1,4-diisopropyl-piperazine-2,3-dithione; Quinoxdt=[1,4]dithiino[2,3-b]quinoxaline-2,3-dithiolate) exhibits a remarkable green emission at 570 nm (room temperature), which is above the lowest excited state. The complex is characterized by negative solvatochromism as well as a high second-order polarizability. Addition of Ag I ions induces 1) hypsochromic shift of the lowest frequencies and 2) reversible quenching of luminescence. The corresponding Ni and Pd complexes have also been prepared and investigated to assist interpretation of optical properties within the triad. Computational studies based on DFT and time-dependent DFT highlight the electronic properties of [Pt(iPr 2 pipdt)(Quinoxdt)]. The preferential site of interaction between the Pt complex and incoming Ag I is evidenced by the shape of the Fukui functions, pointing to the thiolic sulfur and platinum atoms as the most reactive sites towards a soft cation. Calculated optical properties are in agreement with experimental findings. This study sheds light on the structure-property relationship for this class of compounds., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Both linear- and nonlinear-optical properties of Bu 4 N[Pt(L1)(L2)] (1; L1 = [4',5':5,6][1,4]dithiino[2,3-b]quinoxaline-1',3'dithiolato; L2 = (R)-α-MBAdto dithiooxamidate, where (R)-α-MBA = (R)-(+)-α-methylbenzyl) upon HCl addition at room temperature change dramatically: the color turns from deep blue to green; the luminescence switches from deep red to green; the nonlinear-optical response (first hyperpolarizability) increases by a factor of 12. Thus, 1 behaves as a unique multiresponsive optical switch whose properties can be followed by the naked eye.

Ultrafast excited-state dynamics of planar Pt, Pd, and Ni dithione-dithiolato complexes were investigated by transient absorption spectroscopy on the femtosecond-picosecond timescale. All studied complexes show a common photobehaviour, although individual kinetics parameters and quantum yields vary with the metal, the dithione ligand and, namely the solvent (DMF, MeCN). Laser pulse irradiation at 800 nm populates the lowest singlet excited state of a dithiolato → dithione charge transfer character, (1)LL'CT. The optically excited state undergoes a solvation-driven sub-picosecond electronic relaxation that enhances the dithione/dithiolato charge separation. The (1)LL'CT state decays with a 1.9-4.5 ps lifetime by two simultaneous pathways: intersystem crossing (ISC) to the lowest triplet state (3)LL'CT and non-radiative decay to the ground state. ISC occurs on a ∼6 ps timescale, virtually independent of the metal, whereas the rate of the non-radiative decay to the ground state decreases on going from Ni (2 ps) to Pd (3 ps) and Pt (∼10 ps). (3)LL'CT is initially formed as a vibrationally excited state. Its equilibration (cooling) takes place on a picosecond timescale and is accompanied by a competitive decay to the ground state. Equilibrated (3)LL'CT is populated with a quantum yield of less than 50%, depending on the metal: Pt > Pd > Ni. (3)LL'CT is long-lived for Pt and Pd (≫500 ps) and short-lived for Ni (∼15 ps). Some of the investigated complexes also exhibit spectral changes due to vibrational cooling of the singlet (2-3 ps, depending on the solvent). Rotational diffusion occurs with lifetimes in the 120-200 ps range. Changing the dithione (Bz2pipdt/(i)Pr2pipdt) as well as dithiolate/diselenolate (dmit/dsit) ligands has only small effects on the photobehavior. It is proposed that the investigated dithione-dithiolato complexes could act as photooxidants (*E(o) ≈ +1.2 V vs. NHE) utilizing their lowest excited singlet ((1)LL'CT), provided that the excited-state electron transfer is ultrafast, competitive with the picosecond decay. On the other hand, the efficiency of any triplet-based processes would be severely limited by the low quantum yield of the triplet population.

We report the synthesis, characterization, nonlinear-optical (NLO) properties, and density functional theory (DFT) calculations for three nickel diiminedithiolate complexes [Ni(4,4'-R2carboxy-bpy)(L)] [R = methyl, L = 1,2-benzenedithiolate (bdt), 1; R = ethyl, L = 5,6-dihydro-1,4-dithine-2,3-dithiolate (dddt), 2; R = ethyl, L = 1-(N-methylindol-5-yl)ethene-1,2-dithiolate (mi-5edt), 3]. The crystal structure of 1 shows a square-planar coordination for the nickel ion and bond distances consistent with a diiminedithiolate description for the complex. For all complexes, the cyclic voltammetry measurements show two reversible reduction processes (-1.353/-1.380 V and -0798/-0.830 V, respectively) and an anodic wave (+0.372/+0.601 V). The UV-vis spectra present a band around 600-700 nm (ε = 4880-6000 dm(3) mol(-1) cm(-1)) mainly attributed to a charge-transfer highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) transition, which shows a large negative solvatochromic shift, characteristic of push-pull complexes, and is responsible for the NLO properties of these molecules. The charge-transfer character of this electronic transition is confirmed by DFT calculations, with the HOMO mainly centered on the dithiolate moiety and the LUMO on the bpy ligand, with important contribution given by the carboxyl groups (≈13%). Small contributions from the nickel(II) ion are present in both of the frontier orbitals. The carboxyl groups enhance the optical properties of this class of complexes, confirmed by comparison with the corresponding unsubstituted compounds. The second-order NLO properties have been measured by an electric-field-induced second-harmonic-generation technique using a 10(-3) M solution in N,N-dimethylformamide and working with a 1.907 μm incident wavelength, giving for μβ1.907 (μβ0) values of -1095 (-581), -2760 (-954), and -1650 (-618) × 10(-48) esu for 1-3, respectively. These values are among the highest in the class of square-planar push-pull complexes, similar to those found for dithionedithiolate compounds. Moreover, spectroelectrochemical experiments demonstrate the possibility of using these complexes as redox-switchable NLO chromophores.

The mixed-ligand complexes [M(II)(Et2dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et2dazdt = N,N'-diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1-3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P-1), and two independent molecular entities are present in the unit cell. These entities differ in the orientation of the ethyl substituents with respect to the epta-atomic ring. In the C2S2MS2C2 dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the M-S bond distances involving the two ligands are similar, while the C-S bond distances in the C2S2 units exhibit a significant difference in Et2dazdt (dithione) and mnt (dithiolato) ligands. 1-3 show in the visible region one or two moderately strong absorption peaks, having ligand-to-ligand charge-transfer (CT) character with some contribution of the metal, and show negative solvatochromism and molecular quadratic optical nonlinearity, which was determined by the EFISH (electric-field-induced second-harmonic generation) technique. These complexes are redox active and show two reversible reduction waves and one irreversible oxidation wave. Theoretical calculations based on DFT and TD-DFT calculations on complexes 1-3 as well as on [Pt(Bz2pipdt)(mnt)] (4) and [Pt(Bz2pipdt)(dmit)] (5) highlight the factors which affect the optical properties of these second-order redox-active NLO chromophores. Actually, the torsion angle of the dithione system (δ2) inversely correlates either with the oscillator strengths of the main transition of the complexes or with their beta values. The high beta value of 5 can be attributed both to its lowest torsion angles and to the extent of the π system of its dithiolate ligand, dmit.

Mixing [M(Et2dazdt)2](BF4)2 [M = Ni(II), Pd(II), Pt(II); Et2dazdt = N,N'-diethyl-perhydrodiazepine-2,3-dithione] with (Bu4N)2[M(mnt)2] (mnt = maleonitrile-2,3-dithiolate) in CH3CN produces the known mixed ligand dithiolene complex [Ni(Et2dazdt)(mnt)] in the nickel case and ion-pair salts [M(Et2dazdt)2][M(mnt)2] in the palladium (1) and platinum (2) cases. Structural characterization of 2 shows that the anionic (donor) and cationic (acceptor) complexes form an irregular stack that lies in the bc crystallographic plane. The shortest contacts exchanged by the anion and cation molecules within each stack are those occurring through the hydrogen atoms of the CH2 groups of Et2dazdt and the Pt(2)-S(22) segment (d(H(81a)-S(22) = 2.981(3) Å) and the nitrogen atom of the cyano group of mnt and the carbon atom of one of the thione moieties (d(N(12)-C(11) = 3.179(3) Å). The Pt atom of [Pt(mnt)2](2-) is surrounded by two hydrogen atoms of the Et2dazdt ligand, whereas the Pt atom of [Pt(Et2dazdt)2](2+) is surrounded by two carbon atoms of the dithiolate moiety of mnt. Intramolecular interactions are due to contacts exchanged mainly through H-atoms, which are suitable to mediate charge-transfer (CT) interactions. In fact, these salts are characterized by a long wavelength CT peak [λmax = 905 nm (1), 937 nm (2)], which makes them candidates as near-infrared pigments, whose properties are tunable with the redox features of the components, the energy of the NIR absorption being relatable to the driving force of electron transfer from the donor (dianion) to the acceptor (dication). A thorough description of interactions occurring between the complex anions and complex cations has been achieved by investigating the Hirshfeld surface (HS) properties. Computational methods are in agreement with experimental findings and allow us to highlight the electronic features of the components of these CT salts, providing a structure-property relationship, useful in designing new candidates to optimize the desired properties.

Two new isostructural molecular metals-(BDH-TTP)(6)[M(III)(C(5)O(5))(3)]·CH(2)Cl(2) (BDH-TTP = 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, where M = Fe (1) and Ga (2))-have been prepared and fully characterized. Compound 1 is a molecular conductor showing paramagnetic behavior, which is due to the presence of isolated [Fe(C(5)O(5))(3)](3-) complexes with high-spin S = (5)/(2) Fe(III) metal ions. The conductivity originates from the BDH-TTP organic donors arranged in a κ-type molecular packing. At 4 kbar, compound 1 behaves as a metal down to ∼100 K, showing high conductivity (∼10 S cm(-1)) at room temperature. When applying a pressure higher than 7 kbar, the metal-insulator (M-I) transition is suppressed and the compound retains the metallic state down to low temperatures (2 K). For 1, ESR signals have been interpreted as being caused by the fine structure splitting of the high-spin (S = 5/2) state of Fe(III) in the distorted octahedral crystal field from the ligands. At 4 kbar, the isostructural compound 2 behaves as a metal down to ∼100 K, although it is noteworthy that the M-I transition is not suppressed, even at pressures of 15 kbar. For 2, only the signal assigned to delocalized π-electrons has been observed in the ESR measurements.

The donor-acceptor type mixed-ligand complexes [M(Bz(2)pipdt)(dsit)]; dsit = 2-thioxo-1,3-dithiole-4,5-diselenolato (donor); Bz(2)pipdt = 1,4-dibenzyl-piperazine-2,3-dithione (acceptor); M(II) = Ni (1), Pd (2), and Pt (3) were prepared and characterized to investigate the variation of the properties by substituting selenium for sulfur in the donor ligand dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato of the corresponding known complexes. Both these classes of complexes exhibit large negative second-order polarizabilities, amongst the highest values determined so far for metal-complexes, and are potential candidates for redox switchability of the molecular first hyperpolarizability due to the bleaching/restoring of the solvatochromic peak for mono-reduction/oxidation. DFT and TD-DFT calculations on 1-3 allow one to correlate geometries and electronic structures and are in agreement with the observed minor changes following the substitution of selenium for sulfur atoms in the dichalcogenolato ligand. The observed differences can be ascribed to the increased size of the selenium atom leading to increased M-X distances and dipolar moments of the ground state, which are highest for the Pd-derivative in the triad.

The reaction of the croconate dianion (C(5)O(5))(2-) with a Fe(III) salt has led, unexpectedly, to the formation of the first example of a discrete Fe(II)-croconate complex without additional coligands, K(4)[Fe(C(5)O(5))(2)(H(2)O)(2)](HC(5)O(5))(2)·4H(2)O (1). 1 crystallizes in the monoclinic P2(1)/c space group and presents discrete octahedral Fe(II) complexes coordinated by two chelating C(5)O(5)(2-) anions in the equatorial plane and two trans axial water molecules. The structure can be viewed as formed by alternating layers of trans-diaquabis(croconato)ferrate(II) complexes and layers containing the monoprotonated croconate anions, HC(5)O(5)(-), and noncoordinated water molecules. Both kinds of layers are directly connected through a hydrogen bond between an oxygen atom of the coordinated dianion and the protonated oxygen atom of the noncoordinated croconate monoanion. A H-bond network is also formed between the coordinated water molecule and one oxygen atom of the coordinated croconate. This H-bond can be classified as strong-moderate being the O···O bond distance (2.771(2) Å) typical of moderate H-bonds and the O-H···O bond angle (174(3)°) typical of strong ones. This H-bond interaction leads to a quadratic regular layer where each [Fe(C(5)O(5))(2)(H(2)O)(2)](2-) anion is connected to its four neighbors in the plane through four equivalent H-bonds. From the magnetic point of view, these connections lead to an S = 2 quadratic layer. The magnetic properties of 1 have been reproduced with a 2D square lattice model for S = 2 ions with g = 2.027(2) and J = 4.59(3) cm(-1). This model reproduces quite satisfactorily its magnetic properties but only above the maximum. A better fit is obtained by considering an additional antiferromagnetic weak interlayer coupling constant (j) through a molecular field approximation with g = 2.071(7), J = 2.94(7) cm(-1), and j = -0.045(2) cm(-1) (the Hamiltonian is written as H = -JS(i)S(j)). Although this second model might still be improved since there is also an extra contribution due to the presence of ZFS in the Fe(II) ions, it confirms the presence of weak ferromagnetic Fe-Fe interactions through H-bonds in compound 1 which represents one of the rare examples of ferromagnetic coupling via H-bonds.

The mixed-ligand dithiolene complex [Pt(Bz(2)pipdt)(dcbdt)] (1) bearing the two ligands Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione and dcbdt = dicyanobenzodithiolato, has been synthesized, characterized and studied to evaluate its second-order optical nonlinearity. The dithione/dithiolato character of the two ligands gives rise to an asymmetric distribution of the charge in the molecule. This is reflected by structural data showing that in the C(2)S(2)PtS(2)C(2) dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the Pt-S bond distances involving the two ligands are similar, while the C-S bond distances in the C(2)S(2) units exhibit a significant difference in Bz(2)pipdt (dithione) and dcbdt (dithiolato). 1 shows a moderately strong absorption peak in the visible region, which can be related to a HOMO-LUMO transition, where the dcbdt ligand (dithiolato) contributes mostly to the HOMO, and the Bz(2)pipdt one (dithione) mostly to the LUMO. Thus this transition has ligand-to-ligand charge transfer (CT) character with some contribution of the metal and undergoes negative solvatochromism and molecular quadratic optical nonlinearity (μβ(0) = -1296 × 10(-48) esu), which was determined by the EFISH (electric-field-induced second-harmonic generation) technique and compared with the values of similar complexes on varying the dithiolato ligand (mnt = maleonitriledithiolato, dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato). Theoretical calculations help to elucidate the role of the dithiolato ligands in affecting the molecular quadratic optical nonlinearity of these complexes.

Synthesis, characterization, NLO properties, and theoretical studies of the mixed-ligand dithiolene complexes of the nickel triad [M(II)(Bz(2)pipdt)(mnt)] (Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione, mnt = maleonitriledithiolato, M(II) = Ni, 1, Pd, 2, Pt, 3) are reported. Molecular structural characterization of 1-3 points out that four sulfur atoms are in a slightly distorted square-planar geometry. While the M-S bond distances are only slightly different, comparison of the C-C and C-S bonds in the C(2)S(2)MS(2)C(2) core allows us to point out a significant difference between the C-C and the C-S distances in Bz(2)pipdt and mnt. These findings suggest assigning a dithiolato character to mnt (pull ligand) and a dithione one (push ligand) to Bz(2)pipdt. Cyclic voltammetry of 1-3 exhibits two reversible reduction waves and a broad irreversible oxidation wave. These complexes are characterized in the visible region by a peak of moderately strong intensity, which undergoes negative solvatochromism. The molecular quadratic optical nonlinearities were determined by the EFISH technique, which provided the following values μβ(λ) (10(-48) esu) = -1436 (1), -1450 (2), and -1950 (3) converted in μβ(0) (10(-48) esu) = -463 (1), -684 (2), and -822 (3), showing that these complexes exhibit large negative second-order polarizabilities whose values depend on the metal, being highest for the Pt compound. DFT and TD-DFT calculations on 1-3 allow us to correlate geometries and electronic structures. Moreover, the first molecular hyperpolarizabilities have been calculated, and the results obtained support that the most appealing candidate as a second-order NLO chromophore is the platinum compound. This is due to (i) the most extensive mixture of the dithione/metal/dithiolato orbitals, (ii) the influence of the electric field of the solvent on the frontier orbitals that maximizes the difference in dipole moments between the excited and the ground state, and (iii) the largest oscillator strength in the platinum case vs nickel and palladium ones.