A Platinum-Dithiolene Monoanionic Salt Exhibiting Multiproperties, Including Room-Temperature Proton-Dependent Solution Luminescence.

The platinum salt C[PtL2], where C = [(R)-Ph(Me)HC*-NMe3](+) and [PtL2](-) = radical monoanion based on [4', 5': 5, 6][1, 4]dithiino[2,3-b]quinoxaline-1',3'dithiolato, shows a variety of properties both in solution and in the solid state thanks to the electronic and/or structural features of the ligand. The complex crystallizes in the chiral space group P1 due to the presence of the enantiopure cation (R)-Ph(Me)HC*-NMe3(+), and it shows paramagnetic behavior relatable to the [PtL2](-) radical monoanion. This anionic complex is redox active and shows a strong near-infrared absorbance peak at 1085 nm tunable with the oxidation state of the complex. This complex exhibits a proton-dependent emission at 572 nm in solution at room temperature. The excitation band corresponds to the HOMO-1 (π-orbitals of the S2C2S2 system) → LUMO (π-orbitals of the quinoxaline and benzene-like moieties) transition suggesting that emission is mainly ligand centered in character. The luminescent properties are highly unusual, since the emission falls well above the energy of the lowest energy absorption (anti-Kasha behavior). Joint experimental and density functional theory (DFT) and time-dependent DFT studies are discussed to provide a satisfactory structure/property relationship.

Role of the acceptor in tuning the properties of metal [M(II) = Ni, Pd, Pt] dithiolato/dithione (donor/acceptor) second-order nonlinear chromophores: combined experimental and theoretical studies.

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.

Effective one-step gold dissolution using environmentally friendly low-cost reagents.

Digging for gold: Mixtures of tetraethylthiuram disulfide (Et4TDS) and I2 in acetone are capable of dissolving elemental gold and forming valuable metal complexes, in which the stoichiometry depends on the mixture composition. These mixtures can also etch the gold layer homogeneously and selectively from Si/SiO2/Ti/Au thin-layered structures under mild conditions (see figure).

Electrochromic second-order NLO chromophores based on M(II) (M = Ni, Pd, Pt) complexes with diselenolato-dithione (donor-acceptor) ligands.

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.

Influence of the R-substituents on the properties of [Ni(R2pipdt)(dmit)] complexes and crystal structure where R = CH2C6H5.

[Ni(R2pipdt)(dmit)], (R2pipdt = 1,4-disubstituted-piperazine-3,2-dithione, R = CH2C6H5; dmit = 1,3-dithiole-2-thione-4,5-dithiolate) (1b) has been prepared and characterised and the properties compared with those of the known complex 2b belonging to the same class where R = Pr i. Cyclic voltammetry of 1b and 2b was carried out and compared with that of the respective R2pipdt ligand precursors (1a and 2a ). The nature of the R-groups of the pipdt ligand exerts an effect on the redox potentials and confirmed the position of the LUMO as mainly on the R2pipdt part of the complex. Accordingly the low frequency absorption, assigned to the HOMO-LUMO transition which has inter-ligand charge-transfer character, is found for 1b at lower frequency when compared to the corresponding transition of 2b. In situ EPR was carried out on electroreduced radical species of the R2pipdt ligand precursors (1a, 2a ) and corresponding complexes (1b, 2b ). This revealed considerable delocalisation of the unpaired electron on the R2pipdt ligand in 1b and 2b with coupling constants to N and H comparable with those of 1a and 2a . Complex 1b crystallised in the space group Pnma and shows an essentially planar complex (with out-of-plane R groups) pi stacked at a distance of 3.65(1) A. Such a one-dimensional structure is not achieved in the case of 2b, where the complex units are almost parallel and head-to-tail with each other forming dimers and this difference in solid-state packing is apparent in the diffuse reflectance spectrum of each. Plane-wave DFT calculations for 1b revealed a highly one-dimensional band structure with considerable band dispersion along the direction of greatest molecular interaction via pi-stacking.

Pd-Dissolution through a mild and effective one-step reaction and its application for Pd-recovery from spent catalytic converters.

We describe here an innovative method for Pd-dissolution using the reagent N,N'-dimethylperhydrodiazepine-2,3-dithione diiodine adduct which, being safe and powerful, is appealing for practical applications: remarkably almost quantitative Pd-recovery from model spent three-way catalysts has been obtained, showing that the effectiveness of the method is maintained when palladium is contained in a complex system such as a car catalyst, a ceramic material which has undergone severe thermal stress.