Electrochemical Characterization and CO2 Reduction Reaction of a Family of Pyridazine-Bridged Dinuclear Mn(I) Carbonyl Complexes.

Three recently synthesized neutral dinuclear carbonyl manganese complexes with the pyridazine bridging ligand, of general formula [Mn2(µ-ER)2(CO)6(µ-pydz)] (pydz = pyridazine; E = O or S; R = methyl or phenyl), have been investigated by cyclic voltammetry in dimethylformamide and acetonitrile both under an inert argon atmosphere and in the presence of carbon dioxide. This family of Mn(I) compounds behaves interestingly at negative potentials in the presence of CO2. Based on this behavior, which is herein discussed, a rather efficient catalytic mechanism for the CO2 reduction reaction toward the generation of CO has been hypothesized.

Mean-Field Effects on the Phosphorescence of Dinuclear Re(I) Complex Polymorphs.

A computational study rationalizes the different phosphorescence colors of two highly emitting crystal polymorphs of a dinuclear Re(I) complex, [Re2(µ-Cl)2(CO)6(µ-4,5-(Me3Si)2pyridazine)]. The electrostatic interactions between the charge distributions on neighboring molecules inside the crystal are responsible for the different stabilization of the emitting triplet state because of the different molecular packing. These self-consistent effects play a major role in the phosphorescence of crystals made of polar and polarizable molecular units, offering a powerful handle to tune the luminescence wavelength in the solid state through supramolecular engineering.

Highly enantioselective "inherently chiral" electroactive materials based on a 2,2'-biindole atropisomeric scaffold.

Chiral oligothiophene monomers with C 2 symmetry, based on 3,3'-bithiophene atropisomeric cores with high racemization barriers, have recently been shown to provide excellent chiral starting materials with high electroactivity for the easy preparation of enantiopure electroactive films endowed with powerful chirality manifestations. We now introduce an inherently chiral monomer based on a 2,2'-biindole core, as the prototype of a new inherently chiral monomer family, whose properties could be modulable through functionalization of the pyrrolic N atoms. By fast, regular electrooligomerization the new monomer yields inherently chiral films with high, reversible electroactivity and, above all, impressive enantioselectivity towards very different chiral probes, some of pharmaceutical interest, as general-scope electrode surfaces. Such results, while opening the way to a new, attractive inherently chiral selector class, nicely confirm the general validity of the inherent chirality strategy for chiral electrochemistry. Furthermore, the enantioselectivity of the new selectors not only holds with electroactive chiral probes, but also with circularly polarized light components as well as electron spins, resulting in good chiroptical and spin filter performances, which suggests fascinating correlations between the three contexts.

Triarylamine-based hydrido-carboxylate rhenium(i) complexes as photosensitizers for dye-sensitized solar cells.

Two new dyes based on a dinuclear rhenium complex and (E)-3-(5-(4-(bis(2',4'-dibutoxy-[1,1'-biphenyl]-4-yl)amino)phenyl)thiophen-2-yl)-2-cyanoacrylic acid (namely D35) have been investigated as sensitizers for dye sensitized solar cells (DSSCs). Two different pyridazine ligands have been used, namely 4-pyridazine-carboxylic acid for dye 2 ([Re2(µ-H)(-D35)(CO)6(µ-pyridazine-4-COOH)]) and 4-pyridazinyl-butanoic acid for dye 3 ([Re2(µ-H)(-D35)(CO)6(µ-pyridazine-4-C3H6-COOH)]). The performances of these new dyes have been compared with those of the dye containing the bare 4-diphenylaminobenzoic acid, namely TPA, as the ancillary ligand (dye 1). Compared to dye 1, dyes 2 and 3 show an impressive tenfold increase in the absorption intensity in the range of 487-493 nm on TiO2 films, with great improvement of the light harvesting. Cyclic voltammetry experiments, performed on derivatives containing the methyl ester of the pyridazine ligands, show narrow electrochemical band gaps in the range of 1.36-1.84 eV. Solar cells with each dye have been prepared, using both iodide/triiodide and cobalt redox couples as the electrolytes, platinum or carbon as the counter electrodes, and TiO2 or SnO2 as the metal oxide photoelectrodes, respectively. The best DSSC results have been obtained using dye 3, with an overall solar-to-electric conversion efficiency of 3.5%, which greatly overcomes the previous result of 1.0% obtained for dye 1 in a not-optimized setup of the device. The performances of dye 3 are due to the presence of D35 ligand, which further suppresses the recombination of the injected electron with the electrolyte and with the oxidized state of the dye.

Luminescent conjugates between dinuclear rhenium complexes and 17α-ethynylestradiol: synthesis, photophysical characterization, and cell imaging.

Three new luminescent conjugates between dinuclear rhenium complexes and an estradiol, namely E2-Re, are described. The derivatives have the general formula [Re2(µ-Cl)2(CO)6(µ-R-pydz-17α-ethynylestradiol)] (R-pydz = functionalized 1,2-pyridazine), where the estradiol moiety is covalently bound to the ß position of the pyridazine ligand. Different synthetic pathways are investigated, including the inverse-type [4 + 2] Diels Alder cycloaddition reaction between the electron poor 1,2,4,5-tetrazine and 17α-ethynylestradiol for the synthesis of E2-Re1. The three E2-Re conjugates are purified on silica gel and isolated in a spectroscopically pure form in moderate to good yields (28-50%). All the E2-Re conjugates are comprehensively characterized from the spectroscopic and photophysical points of view. Cellular internalization experiments on human MCF-7 and 231 cells are also reported, displaying interesting staining differences depending on the nature of the spacer linking the estradiol unit to the organometallic fragment. Furthermore, the suitability of these conjugates to also stain simple multicellular organisms, i.e. Ciona intestinalis embryos and larvae at different stages of development, is reported here for the first time.

A new catechol-functionalized polyamidoamine as an effective SPION stabilizer.

A synthetic strategy was established for decorating and stabilizing superparamagnetic iron oxide nanoparticles (SPIONs) with a zwitterionic linear polyamidoamine (PAA). The strategy was successfully tested with a PAA coded ISA23 previously found endowed with interesting biological properties, such as biocompatibility, degradability in aqueous media and stealth-like properties when injected in test animals. A post-synthetic functionalization with catechol-bearing moieties of a preformed PAA was successfully carried out. ISA23 was obtained by polyaddition reactions of methyl-piperazine and 2,2-bis(acrylamidoacetic) acid. It was functionalized using nitrodopamine and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide as coupling agent, to randomly form amide bonds with 17% of ISA23 carboxylic groups (ISA23-ND). SPIONs were prepared by a thermal decomposition synthesis in 1-octadecene with oleic acid, and then transferred in water by two distinct ligand exchange procedures: i) the direct displacement of oleate molecules from SPION surface by ISA23 in a biphasic (n-hexane/water) environment; ii) the two-step method involving an intermediate small molecule, tetramethylammonium hydroxide, used as a transient transfer agent, which was in turn exchanged with ISA23-ND in a second exchange step occurring in water. The two-step procedure provided a SPION@PAA nanocomposite more stable than that obtained by the one-step procedure in the presence of an applied external magnetic field. ATR-FTIR spectroscopy, ζ-potential and thermogravimetric analysis (TGA) showed the presence of the ISA23 on the SPION surface. In particular, TGA showed that the ISA23-ND amount on the NPs accounted for 26% of the overall nanocomposite mass. The nanocomposite size was determined by both TEM (21.1±2.9 nm) and DLS measurements (hydrodynamic size 100±28 nm). SPION@ISA23-ND were re-suspended after lyophilization reverting to their pristine dimensions. The SPION@ISA23-ND adsorption of BSA in water, considered as the first stage of phagocytosis, was very low, suggesting that ISA23 could impart stealthiness to SPION@ISA23-ND. 1H-NMR relaxivity measurements showed an r2 value of 158 s-1 mmol-1 L (vs 100 s-1 mmol-1L for Endorem®) at relevant clinical fields for magnetic resonance imaging (from 0.2 to 1.5 T). SPION@ISA23-ND was tested on HeLa cells and their internalization was visualized by reflectance microscopy. Finally, with the aim of prepare a new dual magneto-optical system, a synthetic procedure to decorate SPION@ISA23-ND with a fluorescent dye was devised, even though the emission intensity of the resultant conjugate was lower than expected, possibly due to luminescence quenching caused by the closeness of emitting moieties to the SPION surface.

Glycodendron-rhenium complexes as luminescent probes for lectin sensing.

The design, synthesis and characterization of novel glycoconjugate luminescent probes based on dinuclear rhenium(i) complexes are reported. A multivalent platform bearing different carbohydrate moieties (Glc, Gal and Man) was used to target carbohydrate-binding proteins (lectins), exploiting the unique photophysical characteristics of a Re(i) luminophore for protein sensing. Our results show that these glycoconjugates, non-luminescent in aqueous medium, are able to specifically bind different lectins (ConA and PNA) with a consequent enhancement of emission intensity. These findings suggest the use of Re(i)-based glycoconjugates as switch-on luminescent probe tools in biological applications.

Searching for Models Exhibiting High Circularly Polarized Luminescence: Electroactive Inherently Chiral Oligothiophenes.

Two new inherently chiral oligothiophenes characterized by the atropisomeric 3,3'-bithianaphtene scaffold functionalized with fused ring bithiophene derivatives, namely 4H-cyclopenta[2,1-b3:4b']dithiophene (CPDT) and dithieno[3,3-b:2',3'-d]pyrrole (DTP), were synthesized. The racemates were fully characterized and resolved into antipodes by enantioselective HPLC. The enantiomers were analyzed through different chiroptical techniques: electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) were employed to attribute the absolute configuration (AC). Comparison of experimental and calculated VCD spectra confirmed the DFT calculated conformational characteristics. The compound functionalized with two CPDT units was oxidized with FeCl3 , and ECD and CPL of the resulting material were measured. Circularly polarized luminescence (CPL) was measured to verify if inherently chiral oligothiophenes could be promising systems for chiral photonics applications.

Dirhenium Coordination Complex Endowed with an Intrinsically Chiral Helical-Shaped Diphosphine Oxide.

A one-pot, multicomponent strategy was used to synthesize the first example of the dirhenium carbonyl coordination complex 2, in which the two metal atoms are connected through a chiral helical-shaped diphosphine oxide. Thanks to the flexibility of the helix of helicene 1, complex 2 was isolated in quite a good yield as a stable compound. It was characterized by analytical and spectroscopic techniques as well as by single-crystal X-ray analysis, which confirmed the chemical structure and the peculiar architecture of 2. In addition, computational studies were in agreement with the transitions observed in the experimental UV-vis spectrum, revealing the presence of two bands with maxima at about 520 (metal-to-ligand charge transfer) and 400 nm (IL).

Glyco-functionalized dinuclear rhenium(i) complexes for cell imaging.

The design, synthesis and photophysical characterization of four new luminescent glycosylated luminophores based on dinuclear rhenium complexes, namely Glyco-Re, are described. The derivatives have the general formula [Re2(µ-Cl)2(CO)6(µ-pydz-R)] (R-pydz = functionalized 1,2-pyridazine), where a sugar residue (R) is covalently bound to the pyridazine ligand in the ß position. Different synthetic pathways have been investigated including the so-called neo-glycorandomization procedure, affording stereoselectively glyco-conjugates containing glucose and maltose in a ß anomeric configuration. A multivalent dinuclear rhenium glycodendron bearing three glucose units is also synthesized. All the Glyco-Re conjugates are comprehensively characterized and their photophysical properties and cellular internalization experiments on human cervical adenocarcinoma (HeLa) cells are reported. The results show that such Glyco-Re complexes display interesting bio-imaging properties, i.e. high cell permeability, organelle selectivity, low cytotoxicity and fast internalization. These findings make the presented Glyco-Re derivatives efficient phosphorescent probes suitable for cell imaging application.

Inherently Chiral Spider-Like Oligothiophenes.

The racemate of an inherently chiral "spider-like" octathiophene monomer T83 , in which chirality is generated by torsion in its backbone, was synthesized. The racemate was resolved into configurationally stable antipodes by HPLC on a chiral stationary phase. Electrooxidation of the enantiomers resulted in materials displaying high enantiorecognition ability towards the antipodes of some chiral probes. Moreover, the T83 racemate demonstrated great aptitude to stimulate formation of 3D rigid architectures if used as a cross-linking monomer for molecular imprinting. This feature was exploited to devise a molecularly imprinted polymer-based chemosensor selective for a thymine-adenine oligonucleotide.

Luminescent supramolecular soft nanostructures from amphiphilic dinuclear Re(I) complexes.

Luminescent metallo-surfactants based on highly emissive dinuclear Re(I) complexes have been synthesized combining the peculiar photophysical behaviour of this class of neutral hydrophobic complexes with new properties imparted by hydrophilic chains anchored on the coordinated chromophoric ligand. In solution, the resulting neutral amphiphiles tend to self-assembly in soft structures. The aggregation properties have been thoroughly investigated in dioxane-water mixtures, where all the complexes assembly in globular-like supramolecular architectures with well-defined size (hydrodynamic diameter = 200-400 nm). The morphology of these nano-objects has been completely characterized with Dynamic Light Scattering (DLS) analysis, Scanning Transmission Electron Microscopy (STEM) and cryo-TEM to determine the size, polydispersity, and stability of the nanoparticles in relationship with the structure of the metallo-surfactants. The photophysical properties of both the isolated metal complexes and their aggregates have been investigated by means of UV-Vis absorption, steady-state and time-resolved emission spectroscopy. Noteworthy, the self-assembly properties of the reported luminescent rhenium metallo-amphiphiles can be modulated by solvent polarity. Even more importantly, such aggregation process yielded a small hypsochromic shift of the emission energy accompanied by a sizeable elongation of the excited-state lifetime and an enhancement of the photoluminescence quantum yield, reaching a remarkably high value of 0.20 despite the air-equilibrated aqueous condition. The presented findings endorse novel possibilities for the efficient use of soft-nanostructures based on metallo-amphiphiles in dual (electron and optical microscopy) bio-imaging applications and theranostics where the non-covalent nature of the intermolecular interactions would offer the powerful and unique possibility to reversibly assemble and disassemble imaging agents.

Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

A novel molecular dyad, 1, made of a dinuclear {[Re2(µ-X)2(CO)6(µ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

Dinuclear rhenium complexes as redox-active pendants in a novel electrodeposited polycyclopentadithiophene material.

The novel [Re2(µ-H)(µ-OOC-CPDT)(CO)6(µ-3-Me-pydz)] complex (1; OOC-CPDT = 4H-cyclopenta[2,1-b:3,4-b']dithiophene-4-carboxylate, 3-Me-pydz = 3-methylpyridazine) has been prepared and characterized by single-crystal X-ray diffraction, density functional theory (DFT), and time-dependent DFT computations, UV-vis absorption and emission spectroscopy, and cyclic voltammetry (CV). The measured properties indicate the lack of electronic communication in the ground state between the CPDT and the rhenium diazine moieties. Oxidative electropolymerization of 1, achieved by repeated potential cycling (-0.4 to +1.0 V vs Fc(+)/Fc, in acetonitrile) with different supporting electrolytes, on different electrodes, afforded an electroactive and stable metallopolymer (poly-1). In situ measurements of the mass of the growing film (on a gold electrode, with an electrochemical quartz microbalance) confirmed the regularity of the polymerization process. The polymer exhibits two reversible oxidation peaks of the thiophene chain and a broad irreversible reduction peak (-1.4 V, quite close to that observed for the reduction of monomer 1), associated with a remarkably delayed sharp return peak, of comparable associated charge, appearing in close proximity (+0.3 V) to the first oxidation peak of the neutral polythiophene chain. This charge-trapping effect can be observed upon repeated cycles of p and n doping, and the negative charge is maintained even if the charged electrode is removed from the solution for many hours. Electrochemical impedance spectroscopy showed that the main CV oxidation peak corresponds to facile charge transfer, combined with very fast diffusion of both electrons and ions within the polymer. In summary, poly-1 provides a new example of a metallopolymer, in which the conductive properties of the π-conjugated system are added to the redox behavior of the pendant-isolated complexes.

Inherently chiral macrocyclic oligothiophenes: easily accessible electrosensitive cavities with outstanding enantioselection performances.

Linear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain-end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an "inherently chiral" sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability.

Potential-driven chirality manifestations and impressive enantioselectivity by inherently chiral electroactive organic films.

The typical design of chiral electroactive materials involves attaching chiral pendants to an electroactive polyconjugated backbone and generally results in modest chirality manifestations. Discussed herein are electroactive chiral poly-heterocycles, where chirality is not external to the electroactive backbone but inherent to it, and results from a torsion generated by the periodic presence of atropisomeric, conjugatively active biheteroaromatic scaffolds, (3,3'-bithianaphthene). As the stereogenic element coincides with the electroactive one, films of impressive chiroptical activity and outstanding enantiodiscrimination properties are obtained. Moreover, chirality manifestations can be finely and reversibly tuned by the electric potential, as progressive injection of holes forces the two thianaphthene rings to co-planarize to favor delocalization. Such deformations, revealed by CD spectroelectrochemistry, are elastic and reversible, thus suggesting a breathing system.

Luminescent rhenium and ruthenium complexes of an amphoteric poly(amidoamine) functionalized with 1,10-phenanthroline.

A new amphoteric copolymer, PhenISA, has been obtained by copolymerization of 4-(4'-aminobutyl)-1,10-phenanthroline (BAP) with 2-methylpiperazine and bis(acrylamido)acetic acid (BAC) (6% of phenanthroline-containing repeating units). The copolymer showed excellent solubility in water, where it self-aggregated to give clear nanoparticle suspensions (hydrodynamic diameter = 21 ± 2 nm, by dynamic light scattering (DLS) analysis). The phenanthroline pendants of the polymer stably coordinated either Re(CO)(3)(+) or Ru(phen)(2)(2+) fragments, affording luminescent Re-PhenISA, Re-Py-PhenISA, and Ru-PhenISA polymer complexes, emitting from triplet metal-to-ligand charge transfer ((3)MLCT) excited states (with λ(em) = 608, 571, and 614 nm, respectively, and photoluminescence quantum yields Φ(em) = 0.7%, 4.8%, and 4.1%, in aerated water solution, respectively). DLS analyses indicated that the polymer complexes maintained the nanosize of PhenISA. All the complexes were stable under physiological conditions (pH 7.4, 0.15 M NaCl) in the presence of an excess of the ubiquitous competitor cysteine. In vitro viability assays showed no toxicity of Re-Py-PhenISA and Ru-PhenISA complexes, at concentrations in the range of 0.5-50 µM (calculated on the metal-containing unit), toward HEK-293 (human embryonic kidney) cells. A preliminary investigation of internalization in HEK-293 cells, by means of fluorescence confocal microscopy, showed that Ru-PhenISA enters cells via an endocytic pathway and, subsequently, homogeneously diffuse within the cytoplasm across the vesicle membranes.

Phosphorescent organic light-emitting diodes with outstanding external quantum efficiency using dinuclear rhenium complexes as dopants.

The photophysical and electroluminescence properties of two dinuclear rhenium(I) carbonyl complexes bearing 1,2-diazines are comprehensively investigated. The bromo-bridged complex is successfully used as triplet emitter for the preparation of vacuum-processed OLEDs with outstanding external quantum efficiencies, reaching a value of 10%.

Electrochemical, computational, and photophysical characterization of new luminescent dirhenium-pyridazine complexes containing bridging OR or SR anions.

A series of [Re(2)(µ-ER)(2)(CO)(6)(µ-pydz)] complexes have been synthesized (E = S, R = C(6)H(5), 2; E = O, R = C(6)F(5), 3; C(6)H(5), 4; CH(3), and 5; H, 6), starting either from [Re(CO)(5)O(3)SCF(3)] (for 2 and 4), [Re(2)(µ-OR)(3)(CO)(6)](-) (for 3 and 5), or [Re(4)(µ(3)-OH)(4)(CO)(12)] (for 6). Single-crystal diffractometric analysis showed that the two µ-phenolato derivatives (3 and 4) possess an idealized C(2) symmetry, while the µ-benzenethiolato derivative (2) is asymmetrical, because of the different conformation adopted by the phenyl groups. A combined density functional and time-dependent density functional study of the geometry and electronic structure of the complexes showed that the lowest unoccupied molecular orbital (LUMO) and LUMO+1 are the two lowest-lying π* orbitals of pyridazine, whereas the highest occupied molecular orbitals (HOMOs) are mainly constituted by the "t(2g)" set of the Re atoms, with a strong Re-(µ-E) π* character. The absorption spectra have been satisfactorily simulated, by computing the lowest singlet excitation energies. All the complexes exhibit one reversible monoelectronic reduction centered on the pyridazine ligand (ranging from -1.35 V to -1.53 V vs Fc(+)|Fc). The benzenethiolato derivative 2 exhibits one reversible two-electron oxidation (at 0.47 V), whereas the OR derivatives show two close monoelectronic oxidation peaks (ranging from 0.85 V to 1.35 V for the first peak). The thioderivative 2 exhibits a very small electrochemical energy gap (1.9 eV, vs 2.38-2.70 eV for the OR derivatives), and it does not show any photoluminescence. The complexes containing OR ligands show from moderate to poor photoluminescence, in the range of 608-708 nm, with quantum yields decreasing (ranging from 5.5% to 0.07%) and lifetimes decreasing (ranging from 550 ns to 9 ns) (3 > 4 > 6 ≈ 5) with increasing emission wavelength. The best emitting properties, which are closely comparable to those of the dichloro complex (1), are exhibited by the pentafluorophenolato derivative (3).

Interaction between selected bacterial strains and Arabidopsis halleri modulates shoot proteome and cadmium and zinc accumulation.

The effects of plant-microbe interactions between the hyperaccumulator Arabidopsis halleri and eight bacterial strains, isolated from the rhizosphere of A. halleri plants grown in a cadmium- and zinc-contaminated site, were analysed for shoot metal accumulation, shoot proteome, and the transcription of genes involved in plant metal homeostasis and hyperaccumulation. Cadmium and zinc concentrations were lower in the shoots of plants cultivated in the presence of these metals plus the selected bacterial strains compared with plants grown solely with these metals or, as previously reported, with plants grown with these metals plus the autochthonous rhizosphere-derived microorganisms. The shoot proteome of plants cultivated in the presence of these selected bacterial strains plus metals, showed an increased abundance of photosynthesis- and abiotic stress-related proteins (e.g. subunits of the photosynthetic complexes, Rubisco, superoxide dismutase, and malate dehydrogenase) counteracted by a decreased amount of plant defence-related proteins (e.g. endochitinases, vegetative storage proteins, and ß-glucosidase). The transcription of several homeostasis genes was modulated by the microbial communities and by Cd and Zn content in the shoot. Altogether these results highlight the importance of plant-microbe interactions in plant protein expression and metal accumulation and emphasize the possibility of exploiting microbial consortia for increasing or decreasing shoot metal content.