Davide Espa

Redox-Switchable Chromophores Based on Metal (Ni, Pd, Pt) Mixed-Ligand Dithiolene Complexes Showing Molecular Second-Order Nonlinear-Optical Activity

The synthesis and full characterization of the redox-active nickel triad mixed-ligand dithiolene complexes based on Bz(2)pipdt = 1,4-dibenzylpiperazine-3,2-dithione and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate ligands are reported. These complexes show a reversibly bleacheable solvatochromic peak and a remarkably high negative molecular first hyperpolarizability, whose values depend on the metal being highest for the platinum(II) compound.

Combined experimental and theoretical study on redox-active d8 metal dithione-dithiolato complexes showing molecular second-order nonlinear optical activity.

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.

Mixed-ligand Pt(II) dithione-dithiolato complexes: influence of the dicyanobenzodithiolato ligand on the second-order NLO properties

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.

Structural changes in MII dithione/dithiolato complexes (M = Ni, Pd, Pt) on varying the dithione functionalization

The Ni triad [M(R2pipdt)(dmit)] based on donor/acceptor S,S′ ligands, where R2pipdt = 1,4-diisopropyl-piperazine-2,3-dithione (acceptor) and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato (donor), was completed by preparing and characterizing the Pd(2) and Pt(3) compounds in addition to the already known Ni(1) complex. The rationale behind the work was to compare the properties and structures inside the triad with those of the corresponding Ni(4), Pd(5) and Pt(6) complexes where R = Bz. Minor changes in the properties as redox active nonlinear second-order (NLO) chromophores were observed in solution for the two triads. Instead, different structural features, reflected by changes in the diffuse reflectance spectra, were observed in their crystals on changing R from Bz to Pri in the piperazine ring and also, more surprisingly, inside the triads. 2 (isostructural with 1) and 3 crystallized in monoclinic P21/n and orthorhombic Pbca space groups, respectively. The crystal packings of 2 and 3 are also markedly different. In particular 1 and 2 form head-to-tail dimers whereas 3 forms supramolecular layers characterized by a partial stack between the molecular planes. Large differences in the crystal structures, induced by the diverse number and types of interactions exchanged by the peripheral fragments of the ligands, were found in the Bz-triad. Indeed, the molecules are stacked in a head-to-head and in a head-to-tail fashion in 4 and in 5/6, respectively. Moreover, significantly different packings were observed. The Hirshfeld surface analysis was used to provide a detailed description of the main types of interactions involved in the crystal packing of the six complexes.

New sulfur-oxygen mixed-donor ligand N,N'-dimethyl-piperazine-3-oxo-2-thione (Me2pipto) and its Ni(II) and Fe(II) complexes

Structural and electronic features of the novel title sulfur-oxygen donor ligand Me(2)pipto (1), are discussed in comparison with those of the corresponding dithione ligand Me(2)pipdt. A tuning of the electronic and coordination properties of the ligand, relatable to the soft/hard power of the donor atoms, is achieved. Coordination properties have been checked towards Ni(II) and Fe(III) cations obtaining [Ni(Me(2)pipto)(3)](BF(4))(2) (2) and [Fe(Me(2)pipto)(3)](BF(4))(2) (4) complexes, which show significant differences when compared with the corresponding reaction products when using Me(2)pipdt.

From trash to resource: a green approach to noble-metals dissolution and recovery

Abstract A process based on the lixiviant properties of organic mixtures of dihalogen/S,S-ligands, N,N′-dimethyl-perhydrodiazepine-2,3-dithione (Me2dazdt) and tetraalkylthiuramdisulphide (Et4TDS) in the presence of diiodine, for gold recovery from the non-ferrous metal fraction of real shredded waste electric and electronic equipment (WEEE), is presented here. Selective dissolution of metals is achieved through a sequence of three steps where the oxidation of different kinds of metals is achieved by using: (1) refluxing water solutions of HCl 1:5 under Ar atmosphere (Sn, Zn, etc.); (2) water solutions of NH3/(NH4)2SO4 mixtures in the presence of H2O2 on the resting sample (Cu, Ag); and (3) acetone solutions of Me2dazdt or Et4TDS/I2 mixtures on the final residue (Au). Each step is followed by a further treatment for: (1) metal recovery, in the case of Au, Cu, Ag; and (2) inertization, in the case of heavy metals. As a whole, the process is very promising for effective recovery of gold and other valuable noble-metals and for using non harmful reagents in mild conditions.

A nonlinear optical active polymer film based on Pd(II) dithione/dithiolate second-order NLO chromophores

A film of [Pd(R2pipdt)(dmit)] (1), where R2pipdt = 1,4-didodecyl-piperazine-2,3-dithione (acceptor) and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate (donor) incorporated into a polymethylmethacrylate (PMMA) matrix, showing a good second-harmonic generation, has been prepared for the first time in the class of dithione-dithiolate 2nd order NLO-chromophores. Moreover full characterization of 1, including molecular second-order NLO properties in solution, is reported.

Uncommon Optical Properties and Silver-responsive Turn-off/on Luminescence in a Pt(II) heteroleptic dithiolene complex

Complex [Pt(iPr2 pipdt)(Quinoxdt)] (iPr2 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 AgI 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(iPr2 pipdt)(Quinoxdt)]. The preferential site of interaction between the Pt complex and incoming AgI 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.

Tuning the oxidation state and magnetic and coordination behaviour of iron and cobalt complexes by O/S variation in mono-thio and dithio-oxamide chelating ligands

New iron and cobalt complexes coordinated with the ligands Me2pipto (N,N′-dimethyl-piperazine-3-oxo-2-thione) and Me2pipdt (N,N′-dimethyl-piperazine-2,3-dithione, S,S′), differing in one sulphur substituting the oxygen atom, have been prepared and characterized. The reaction with Me2pipto and iron salts affords the heteroleptic [FeIII(Me2pipto)2Cl2]+ or the homoleptic [FeII(Me2pipto)3]2+ cationic complexes (isolated as tetrafluoroborate salts 1 and 2) depending on the employed iron source: FeCl3 or Fe2(SO4)3 respectively. The corresponding reaction with CoCl2 as the metal source allowed us to obtain [CoII(Me2pipto)3](BF4)2 (3). By reacting FeCl3, Me2pipto and KSCN in the molar ratio 1 : 1 : 4, [FeIII(Me2pipto)(NCS)4]− is obtained and isolated as a Ph4P+ salt (4). Upon using the Me2pipdt ligand, the reaction with FeCl3 affords [FeII(Me2pipdt)3]2+ which is isolated as a tetrafluoroborate salt (5). The same cation is found in the polyiodide salt [FeII(Me2pipdt)3](I3)1.8(I)0.2 (6) obtained by reacting iron-metal powders with Me2pipdt and I2 mixtures. Through a similar reaction by using cobalt-metal powders, [CoIII(Me2pipdt)3]2(I3)2(I)4·2I2 (7) is obtained. Structural results show that in all these compounds the metal ions are in a pseudo-octahedral coordination geometry and that bond distances are consistent with the presence of iron(III) in 1 and 4 and iron(II) in 2 and cobalt(III) in 7. Magnetic susceptibility measurements show that the metals are in a high spin state in all Me2pipto complexes and a low spin state in Me2pipdt. The observed differences are relatable to the different σ-donor and π-acceptor capabilities of the ligands tuned by the S and O donor atoms. Results from DFT calculations using B3LYP and OLYP as functionals are in agreement with the observed magnetic behaviour of the complexes.

Ultrafast Electronic Relaxations in Metal Mixed-Ligand Dithiolene Complexes

Here we present our first results on the fs to ps relaxations in a series of square-planar d8 metal mixed-ligand dithiolene complexes, investigated with fs time resolved broadband transient absorption spectroscopy