Angela Serpe

• PhD
• Professor (Associate) at University of Cagliari

Waste Electrical and Electronic Equipment (WEEE or e-waste) has emerged as a formidable global waste stream, reflecting the mounting demand for technology in our interconnected world. Over the past two decades, besides a world facing a rapid digital, e-mobility, and green energy transition, there has been a growing recognition across the globe, amo...

In a global context characterized by severe environmental problems and increasing resource scarcity, waste represents both a challenge and an opportunity. This study aims to demonstrate with a real case the potential for optimizing the waste valorization action attainable through the synergic application of different treatments to residues of equal...

Permanent magnets (PMs) containing rare earth elements (REEs) can generate energy in a sustainable manner. With an anticipated tenfold increase in REEs demand by 2050, one of the crucial strategies to meet the demand is developing of efficient recycling methods. NdFeB PMs are the most widely employed, however, the similar chemical properties of Nd...

Since 2004, the Italian Ministry of Education, University and Research (MIUR), the Conference of Science and Technology Headmasters, and Confindustria, have been promoting the National Plan for Scientific Degrees (PLS) aimed at supporting students in acquiring scientific skills better responding to contemporary society challenges and increasing voc...

Three-way catalysts (TWCs) are widely used in vehicles to convert the exhaust emissions from internal combustion engines into less toxic pollutants. After around 8–10 years of use, the declining catalytic activity of TWCs causes them to need replacing, leading to the generation of substantial amounts of spent TWC material containing precious metals...

Electronic waste (e-waste) is one of the fastest-growing waste streams in the world and Europe is classified as the first producer in terms of per capita amount. To reduce the environmental impact of e-waste, it is important to recycle it. This work shows the possibility of reusing glassy substrates, derived from the MW-assisted acidic leaching of...

Peculiar chemical, mechanical, and magnetic properties make cobalt a key metal for a variety of “hot” applications like the cathode production of Li-ion batteries. Cobalt is also the preferred metallic binder for tungsten carbide tool manufacturing. The recent increasing criticality of cobalt and tungsten is driving the interest of manufacturers an...

Peculiar chemical, mechanical and magnetic properties make cobalt a key metal for a variety of “hot” applications like cathode production of Li-ion batteries. Cobalt is also the preferred metallic binder for tungsten carbide tools manufacturing. The recent increasing criticality of cobalt and tungsten is driving the interest of manufacturers and re...

Peculiar chemical, mechanical and magnetic properties make cobalt a key metal for a variety of “hot” applications like cathode production of Li-ion batteries. Cobalt is also the preferred metallic binder for tungsten carbide tools manufacturing. The recent increasing criticality of cobalt and tungsten is driving the interest of manufacturers and re...

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 3d-4f architectures depending on the nature of the counteranion, irrespective of the size of the 4f metal ion. Tetranuclear oligomers with a...

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...

N,N'-Dialkylpiperazine-2,3-dithiones (R2pipdt) were recognized as a class of hexa-atomic cyclic dithiooxamide ligands with peculiar charge-transfer donor properties toward soft electron-acceptors such as noble metal cations and diiodine. The latter interaction is nowadays better described as halogen bonding. In the reaction with diiodine, R2pipdt u...

Despite the greater awareness of elemental sustainability and the benefits of the circular economy concept, much waste electrical and electronic equipment (WEEE) is still destined for landfill. Effective methods for valorizing this waste within our society are therefore imperative. In this contribution, two gold(III) complexes obtained as recovery...

Rare-earth elements are widely used in high-end technologies, the production of permanent magnets (PMs) being one of the sectors with the greatest current demand and likely greater future demand. The combination of Nd and Dy in NdFeB PMs enhances their magnetic properties but makes their recycling more challenging. Due to the similar chemical prope...

The reaction between the binuclear cobalt complex, [Co2(Et2dtc)5]⁺, and Me2pipdt and Ph2pipdt ligands has provided almost quantitatively the cobalt tris-chelate heteroleptic complexes [Co(Et2dtc)2(R2pipdt)]BF4 (1 and 2). The molecular structure of 2 shows the metal in a distorted octahedral geometry. The nature of the bonding in these complexes has...

The agro-industrial sector makes a high contribution to greenhouse gas emissions; therefore, proper waste management is crucial to reduce the carbon footprint of the food chain. Hydrothermal carbonization (HTC) is a promising and flexible thermochemical process for converting organic materials into energy and added-value products that can be used i...

In this mini-review recent progress in studies on heteroleptic d⁸-metal dithiolene complexes with a D–M–A donor–π–acceptor electronic structure showing non-linear and linear optical properties, are presented. The ligands, formally dithiolenes, consist in a variety of donors (dithiolato) and acceptors (dithioxamide and dithioxamidate), differing for...

Panchromatic single-component pure white light generation with a PLQY of ~14.5% is obtained from a dysprosium complex with the 5,7-dichloro-8-quinolinol ligand (HClQ) thanks to a peculiar orange-red excimer-like emission induced...

Hydrothermal carbonization (HTC) is a promising thermochemical process for converting organic materials into added-value products that can be used in different applications. In this work, grape marcs and dephenolized grape marcs were hydrothermally treated at 220 °C for 1 h and the resulting hydrochars and process water were investigated to test su...

The direct use in catalysis of precious metal recovery products from industrial and consumer waste is a very promising recent area of investigation. It represents a more sustainable, environmentally benign, and profitable way of managing the low abundance of precious metals, as well as encouraging new ways of exploiting their catalytic properties....

In the context of new efficient and safe leaching agents for noble metals, this paper describes the capability of the Me2pipdt/I2 mixture (where Me2pipdt = 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 present study, combined recovery of biohydrogen and polyhydroxyalkanoate (PHA) from sheep cheese whey (SCW) was investigated through a 3-stage treatment (dark fermentation, PHA-accumulating microorganisms selection and PHA accumulation process). Batch dark fermentation (DF) tests (I stage) were performed on raw SCW adopting two different pH...

Hard Metals (HM) production plays a fundamental role in economy and technological development. Due to the criticality of its main raw materials, W and Co, a sustainable HM waste recycling is hence desirable for both environmental and economic reasons and strongly encouraged by European waste management directives. This work describes a new solvomet...

The waste stream of obsolete electronic equipment grows exponentially, creating a worldwide pollution and resource problem. Electrical and electronic waste (e-waste) comprises a heterogeneous mix of glass, plastics (including flame retardants and other additives), metals (including rare Earth elements), and metalloids. The e-waste issue is complex...

The present work shows the capability of Maleic Acid solutions to tune the amount of Co in cemented carbide-based recovery powders with a Co content exceeding the threshold (10% Co) for industrial manufacturing in Hard Metal production and required by safety regulations. Maleic acid solutions react promptly and selectively in very mild conditions (...

Structures and properties, including second-order non-linear optical properties in solution and in polymethylmethacrylate (PMMA) films, of new nickel heteroleptic Donor-Acceptor dithiolene complexes are reported here ([Ni(Bn 2 pipdt) L1 - 4 ], 1 - 4 ). The acceptor dithione...

[PdI2(Me2dazdt)] is obtained from palladium powder via a 100% atom economical Pd(0) leaching reaction using Me2dazdt (N,N’-dimethyl-perhydrodiazepine-2,3-dithione) and iodine. This complex is a versatile starting point for ligand exchange reactions with (di)phosphines, yielding trans-[PdI2(PPh3)2] and [PdI2(dppe)] (dppe = 1,2-bis(diphenylphosphino)...

An extensive investigation on the NMs content in different classes of WPCBs (Random Access Memories, RAMs; Network Interface Controllers, NICs; motherboards; TV, DVD/CD player, hard-drive and mobile phone PCBs) has been performed to define the most appropriate case study and provide a robust database useful for workers in the waste valorisation fie...

Hybrid organic-inorganic luminescent lanthanide-based nanomaterials are currently attracting great interest for a variety of applications from bioimaging/sensing to optics and photonics. Herein we present a concept model system based on purely silica-based core-shell nanoparticles (NPs) where luminescent Eu³⁺ ions are confined into a thin silica la...

Obsolete or end-of-life electrical and electronic equipment waste streams continue to grow exponentially, creating a worldwide pollution problem. E-waste comprises a heterogeneous mix of hazardous and non-hazardous metals, metalloids, glass, plastics, flame-retardants and valuable materials (e.g. gold, silver, copper, palladium, platinum and indium...

The complex [Pt(i‐Pr2pipdt)(Quinoxdt)] (i‐Pr2pipdt = 1,4‐di‐isopropyl‐piperazine‐2,3‐dithione; Quinoxdt= [1,4]dithiino[2,3‐b]quinoxaline‐2,3‐dithiolate) exhibits a remarkable green emission at 550 nm (room temperature), which is above the lowest excited state. The complex is characterized by negative solvatochromism as well as a high second‐order p...

The catalytic activity of a series of neutral and cationic, homo- and heteroleptic, mono- and bimetallic palladium(II) compounds based on dithiocarbamate and dithiooxamide S,S-donor ligands is described. High activity was observed in the regio- and chemo-selective C-H functionalization of benzo[h]quinoline to 10-alkoxybenzo[h]quinoline and 8-methyl...

Both linear- and nonlinear-optical properties of Bu4N[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 re...

The structure-property relationship for the class of square-planar d⁸ metal heteroleptic dithiolene complexes, which exhibit negative solvatochromism and high molecular first hyperpolarizability, is discussed on the basis of experimental and theoretical results. The role of each ligand and of the metal in the electronic distribution, is highlighted...

Pd dissolution capabilities of a variety of organic triiodides (OrgI3) in organic solvent, where Org⁺ = 3,5-bis(phenylamino)-1,2-dithiolylium [(PhHN)2DTL⁺], 3,5-bis(morpholino)-1,2-dithiolylium (Mo2DTL⁺); tetrabuthylammonium (TBA⁺); and tetraphenylphosphonium (Ph4P⁺), toward the crude metal and model-spent three-way catalyst (TWC), are described he...

Er x Yb (3-x) Q 9 ( 1 , x = 1, 2), NdYb 2 Q 9 ( 2 ), NdEr 2 Q 9 ( 3 ) and NdErYbQ 9 ( 4 ), have been obtained through a simple molecular strategy, by controlling reactant stoichiometry. In 2-4 , the templating effect of the molecular framework allows to control the metal distribution across the coordination sites where the central position is occup...

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...

The successful production of a nanostructured and highly dispersed Pd-TiO2 photo-catalyst, by using the [Pd(Me2dazdt)2]I6 (Me2dazdt=N,N'-dimethyl-perhydrodiazepine-2,3-dithione) salt, obtained through selective and safe recovery of palladium from model exhaust Three-Way Catalysts (TWC), is reported here. The photo-catalyst prepared by direct photo-...

Nd-to-Yb energy transfer (ET) at molecular level has been investigated in the novel heterobimetallic NdYb2Q9 (Q = 8-quinolinolate) complex where the Q ligand works as high cross-section optical antenna. The remarkable ion size-driven templating effect of Nd3+ allows for a good control of molecular speciation through a simple one-pot synthetic proce...

A simple change of one chloro substituent on the chloranilate ligand with a cyano group dramatically affects the electronic properties of the anilate moiety inducing unprecedented luminescence properties in the class of anilate-based ligands and their metal complexes. Here we report on the optimized synthesis and full characterization, including ph...

Homo- and heterobimetallic homoleptic complexes of general formula ErxYb3-xQ9 (Q = 8-quinolinolato; x = 0, 1; x = 1, 2; x = 2, 3) and the corresponding heteroleptic complexes ErxYb3-xQ8NO3 (x = 0, 1b; x = 1, 2b; x = 2, 3b), where one Q ligand is replaced by a nitrate anion, have been synthesized, and fully characterized by means of compositional (E...

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 wa...

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...

An overview of the different strategies proposed for the preparation of heterolanthanide assemblies suitable to work as (multi-) functional materials, highlighting their structure/property relationship, is provided. Three classes of compounds are selected: multi-dimensional coordination frameworks, polynuclear discrete molecules and flexible large...

A unique example of discrete molecular entity Ndy Erx Yb3-(x+y) Q9 (1) (Q=quinolinolato) containing three different lanthanides simultaneously emitting in three different spectral regions in the NIR, ranging from 900 to 1600 nm, has been synthesized and fully chararacterized. A simple molecular strategy based on tuning metal composition in the Ln3...

An effective and sustainable method for the selective leaching of metals from the non-ferrous metal fraction of Waste Electric and Electronic Equipments (WEEE), is described here. This method consists in a sequence of steps which involve the selective leaching of the different metals from the shredded sample by using environmental friendly lixivian...

Invited for the cover of this issue is the group of Flavia Artizzu and Paola Deplano at the University of Cagliari (Italy). The image depicts the Three Graces of Canova, illustrating an assembly of three entities, as does the Ln3Q9 molecular framework with three different NIR-luminescent lanthanide ions. Read the full text of the article at 10.1002...

Supramolecular non-covalent interactions, which drive the molecular packing of crystalline functional molecular materials, can be employed as effective tools for mediating magnetic exchange interactions. Specifically, directional hydrogen- and halogen-bonds and  interactions can be used to design materials in which the magnetic exchange pathways...

Sol-gel silica thin films embedding an ytterbium quinolinolato complex ( YbClQ 4 ) have been obtained using different alkoxides. Homogeneous, crack- and defect-free thin films of optical quality have been successfully deposited on glass substrate by dip-coating. The silica thin films have been characterized by time-resolved photoluminescence....

Here we report on the synthesis and characterization of two isostructural mononuclear complexes of formula [(Ph)4P]3[M(H2An)3]·6H2O (M = Fe(III) (1) or Cr(III) (2); H2An = H2C6O42– = dianion of 3,6-dihydroxy-1,4-benzoquinone (DHBQ)) as suitable metallotectons for the preparation of H-bonded supramolecular architectures. The crystal structure of 1 c...

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 th...

Electrocrystallization of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) in the presence of the tris(chloranilato)ferrate(III) [Fe(Cl2An)3](3-) paramagnetic chiral anion in different stoichiometric ratios and solvent mixtures afforded three different hybrid systems formulated as [BEDT-TTF]3[Fe(Cl2An)3]·3CH2Cl2·H2O (1), δ-[BEDT-TTF]5[Fe(Cl2An)3]·4...

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 he...

Here we report on new tris(haloanilato)metallate(iii) complexes with general formula [A]3[M(X2An)3] (A = (n-Bu)4N(+), (Ph)4P(+); M = Cr(iii), Fe(iii); X2An = 3,6-dihalo derivatives of 2,5-dihydroxybenzoquinone (H4C6O4), chloranilate (Cl2An(2-)), bromanilate (Br2An(2-)) and iodanilate (I2An(2-))), obtained by a general synthetic strategy, and their...

[HMe2pipdt]I3 (Me2pipdt = N,N′-dimethyl-piperazine-2,3-dithione, 1) is capable to quantitatively dissolve elemental Cd and Hg to produce in a one-step reaction the [CdI(Me2pipdt)2]I3 (2) and [HgI2(Me2pipdt)] (3) complexes. Crystals of 2 and 3 have been structurally characterized and crystallize in the P-1 and C2/c space group respectively. In 2 Cd(...

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...

Combined chemical/photophysical studies on the mixed Yb−Er trinuclear lanthanide quinolinolato compound Yb2ErQ9 and on the corresponding Yb3Q9 analogue have been performed. In the mixed-metal molecular species, the ligands, acting as a bridge, allow the two metals to lie at optimal distance for direct Yb-to-Er resonance energy transfer, which reach...

A simple change of the substituents in the bridging ligand allows tuning of the ordering temperatures, Tc, in the new family of layered chiral magnets A[M(II)M(III)(X2An)3]·G (A = [(H3O)(phz)3](+) (phz = phenazine) or NBu4(+); X2An(2-) = C6O4X2(2-) = 2,5-dihydroxy-1,4-benzoquinone derivative dianion, with M(III) = Cr, Fe; M(II) = Mn, Fe, Co, etc.;...

Digging for gold: Mixtures of tetraethylthiuram disulfide (Et4 TDS) 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 unde...

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 () and platinum () c...

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))...

The [Yb(5,7ClQ)2(H5,7ClQ)2Cl] (1) complex, that exhibits dual-luminescence in the visible (ligand-centered) and in the NIR (Yb-centered), has been incorporated into a silica sol–gel glass obtaining 1-doped glassy material which is optically transparent and homogeneous and with good mechanical properties. The doped sol–gel glass can be considered a...

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 (), Pd (), and Pt () were prepared and characterized to investigate the variation of the properties by substituting selenium for sulfur in the donor lig...

K4[Fe(C5O5)2(H2O)2][C5O5H]2·4H2O represents one of the very few examples of Fe(II)−croconate complexes and the first discrete one without additional coligands. It shows an extended network of moderate−strong H-bonds that leads to the formation of quadratic layers that represents one of the rare examples of ferromagnetic coupling mediated through H-...

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 asymmet...

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. In particular we studied two isoelectronic series (Ni, Pd, Pt) of two homologous complexes to clarify the role of the central atom, the...

The anhydrous hepta-coordinated [Yb(5,7ClQ)2(H5,7ClQ)2Cl] complex bearing in the lanthanide coordination sphere two quinolinolato, two quinolinols in the zwitterionic form and one chloride, has been synthesized and fully characterized. This compound exhibits dual luminescence in the near-IR (metal-centered) and in the visible (ligand-centered) spec...

Studies addressed to a deep understanding of the structure/property relationship on the near infrared (NIR)-emissive erbium–quinolinolate complexes, which are of interest for low-cost photonic systems, are reviewed. The role of the 8-quinolinolate ligand (Q), which studies also as sensitizer to overcome the weak absorptivity of lanthanide ion, is d...

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 sulf...

The one-pot synthesis and structural characterization of two new complexes of the croconato ligand (C5O5)2− with the Ga(III) and Er(III) metal ions are reported. The mononuclear tris-chelated (n-Bu4N)3[Ga(C5O5)3], 1, which exhibits an octahedral geometry, is present as Δ and Λ enantiomers in equal amounts; the K2[Er(C5O5)(μ-SO4)(OH2)4]2 complex, 2,...

A variety of silver(I) neutral complexes differing in stoichiometries and/or crystallographic arrangements have been obtained by reacting [HMe2pipdt]I3 (1) (Me2pipdt = N,N′-dimethyl-piperazine-2,3-dithione) with silver as a metal powder and as 1+ metal ion. Once dissolved in THF, 1 reacts with silver powder, affording complexes of different ligand/...

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 hy...

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...

Introduction Square‐Planar d ⁸ Metal Dithiolenes Molecular Conductors, Magnets and Conducting/Magnetic Hybrid Materials Perspectives Acknowledgments

Molecule-based materials are extremely versatile materials as they can be built from specifically designed building blocks with the desired size, shape, charge and electronic properties which determine their intermolecular interactions and, thus, their organization in the solid. The intermolecular interactions, therefore, in particular van der Waal...

The structure/property relationship of square-planar d8 metal push/pull mixed-ligand dithiolene complexes is discussed to provide suitable tools to chemists for tailoring compounds with predictable optical properties. These complexes exhibit a typical HOMO–LUMO electronic transition which falls at low energies (vis–NIR region). Substituents at the...

In this paper we present an experimental and theoretical study to investigate the electronic structures of [ML₂]⁻ (M(III) = Cu, L = pdt and pds, pyrazine-2,3-dithiolate and -diselonate; M(III) = Au, L = pds) with the aim of elucidating the nature of the bonding and to establish the innocent-noninnocent character of the ligand in these complexes. Ca...

The synthesis, structure and spectroscopic properties of a new class of asymmetric nickel dithiolene complex containing pendent thiophene units [Ni(R(2)pipdt)(b-3ted)] are described {R = Bz (3), Pr-i (4); pipdt = piperazine-3,2-dithione; b-3ted = bis(3-thienyl)-1,2-ethylenedithiolene}. X-ray crystallography of both neutral species shows planar nick...

AbstractThe novel [Ni(Me2pipdt)(dddt)] complex based on the Me2pipdt (1,4-dimethylpiperazine-3,2-dithione) and dddt (5,6-dihydro-1,4-dithine-2,3-dithiolate) ligands has been synthesised and characterised. Structural data, vibrational marker, solvatochromic behaviour of the typical absorption in the near infrared region, and approximate theoretical...

Experimental and theoretical results on the novel [Pd(Me2pipdt)(dmit)] complex (1) based on the push Me2pipdt (1,4-dimethyl-piperazine-3,2-dithione) and pull dmit (1,3-dithiolo-2-thione-4,5-dithiolato), show that an unbalanced electron distribution at the dithiolene core occurs. The presence of a solvatochromic absorption at low energy, shifted to...

In this paper, we present a theoretical study based on DFT methods using functionals implemented in Gaussian03, to obtain geometry optimizations, harmonic frequencies, IR intensities and Raman scattering activities of the triad [Ni(tdas)2]z [z = 0 (); z = 1- (); z = 2- ()] and of [Au(tdas)2]- (3) with the aim of elucidating the nature of the bondin...

The synthesis, X-ray structure and magnetic properties of polynuclear Cr(III) complexes with the croconate ligand (C5O5(2-)) are reported: [Cr(mu-C5O5)(micro-OH)(OH2)2]2 x 6H2O (, orthorombic, space group Cmca, a = 6.741(7) A, b = 18.841(9) A, c = 16.886(9) A, V = 2145(3) A3) shows a dinuclear structure with two mu-OH hydroxo group and two ligand m...

The synthesis and structural characterization of the neutral gadolinium tetrakis-type complex with 5,7-dichloro-8-quinolinolato (H5,7ClQ) ligands, [Gd(5,7ClQ)2(H5,7ClQ)2Cl], is reported. The GdIII ion is epta coordinated to one chloride ion and to four ligands: two N,O-chelated monoanions and two as zwitterionic (+NH and O–) monodentate oxygen dono...

Commonly involved in the recovery/refining processes of noble metals (NMs), coordination chemistry is now required by new legislation to face requirements in the selection of ligands that must combine effectiveness with low environmental impact, in order to balance sustainability with economic development for conventional applications and for the r...

[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 tha...

Erbium quinolinolates, commonly assumed to be mononuclear species with octahedral co-ordination geometry, have been proposed as promising materials for photonic devices but difficulties in obtaining well defined products have so far limited their use. We report here the conditions to obtain in high yields three different kinds of pure neutral erbiu...

The paramagnetic and chiral anion [Fe(C5O5)3]3- (C5O52-=croconate) has been combined with the organic donor BEDT-TTF (=ET=bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor with the first chirality-induced alpha phase, alpha-(BEDT-TTF)5[Fe(C5O5)3].5H2O (1), and one of the few known paramagnetic molecular metals,...