Challenges in the Direct Detection of Chirality-induced Spin Selectivity: Investigation of Foldamer-based Donor-acceptor Dyads.

Over the past two decades, the chirality-induced spin selectivity (CISS) effect was reported in several experiments disclosing a unique connection between chirality and electron spin. Recent theoretical works highlighted time-resolved Electron Paramagnetic Resonance (trEPR) as a powerful tool to directly detect the spin polarization resulting from CISS. Here, we report a first attempt to detect CISS at the molecular level by linking the pyrene electron donor to the fullerene acceptor with chiral peptide bridges of different length and electric dipole moment. The dyads are investigated by an array of techniques, including cyclic voltammetry, steady-state and transient optical spectroscopies, and trEPR. Despite the promising energy alignment of the electronic levels, our multi-technique analysis reveals no evidence of electron transfer (ET), highlighting the challenges of spectroscopic detection of CISS. However, the analysis allows the formulation of guidelines for the design of chiral organic model systems suitable to directly probe CISS-polarized ET.

Evidence of crystal packing effects in stabilizing high or low spin states of iron(ii) complexes with functionalized 2,6-bis(pyrazol-1-yl)pyridine ligands.

The molecular structures and magnetic properties of homoleptic iron(ii) compounds [Fe(bpp-COOMe)2](ClO4)2 (1) and [Fe(bpp-triolH3)2](ClO4)2 (2) have been investigated to ascertain their spin crossover (SCO) behaviour. In these hexacoordinated complexes, the bpp (2,6-bis(pyrazol-1-yl)pyridine) ligands adopt a mer-mer coordination mode and carry COOMe or C(O)NHC(CH2OH)3para substituents, respectively, on the central pyridyl ring. In spite of the almost equal donor power of the ligands to the iron(ii) centre, the two compounds feature different spin state configurations at room temperature. Compound 1 displays a highly-distorted octahedral environment around the iron(ii) centre, which adopts a high spin (HS) state at all temperatures, even under an external applied pressure up to 1.0 GPa. By contrast, 2 is characterized by a more regular octahedral coordination around the metal ion and exhibits a low spin (LS) configuration at or below room temperature. However, it shows a thermally-induced SCO behaviour at T > 400 K, along with Light-Induced Excited Spin State Trapping (LIESST) at low temperature, with TLIESST = 38 K. Since DFT (U)M06/6-311+G(d) geometry optimizations in vacuo indicate that both complexes should adopt a HS state and a highly-distorted coordination geometry, the stabilization of a LS configuration in 2 is ultimately ascribed to the effect of intermolecular hydrogen bonds, which align the [Fe(bpp-triolH3)2]2+ cations in 1D chains and impart profound differences in the geometric arrangement of the ligands.

Synthesis, structural characterization and biological evaluation of 4'-C-methyl- and phenyl-dioxolane pyrimidine and purine nucleosides.

Nucleoside analogues play an important role in antiviral, antibacterial and antineoplastic chemotherapy. Herein we report the synthesis, structural characterization and biological activity of some 4'-C -methyl- and -phenyl dioxolane-based nucleosides. In particular, α and ß anomers of all natural nucleosides were obtained and characterized by NMR, HR-MS and X-ray crystallography. The compounds were tested for antimicrobial activity against some representative human pathogenic fungi, bacteria and viruses. Antitumor activity was evaluated in a large variety of human cancer cell-lines. Although most of the compounds showed non-significant activity, 23α weakly inhibited HIV-1 multiplication. Moreover, 22α and 32α demonstrated a residual antineoplastic activity, interestingly linked to the unnatural α configuration. These results may provide structural insights for the design of active antiviral and antitumor agents.

UHV deposition and characterization of a mononuclear iron(III) ß-diketonate complex on Au(111).

The adsorption of the sterically hindered ß-diketonate complex Fe(dpm)3, where Hdpm = dipivaloylmethane, on Au(111) was investigated by ultraviolet photoelectron spectroscopy (UPS) and scanning tunnelling microscopy (STM). The high volatility of the molecule limited the growth of the film to a few monolayers. While UPS evidenced the presence of the ß-diketonate ligands on the surface, the integrity of the molecule on the surface could not be assessed. The low temperature STM images were more informative and at submonolayer coverage they showed the presence of regular domains characterized by a flat morphology and height of ≈0.3 nm. Along with these domains, tetra-lobed features adsorbed on the kinks of the herringbone were also observed. DFT-simulated images of the pristine molecule and its possible decomposition products allowed to assess the partial fragmentation of Fe(dpm)3 upon adsorption on the Au(111) surface. Structural features with intact molecules were only observed for the saturation coverage. An ex situ prepared thick film of the complex was also investigated by X-ray magnetic circular dichroism (XMCD) and features typical of high-spin iron(III) in octahedral environment were observed.

Single-ion and molecular contributions to the zero-field splitting in an iron(III)-oxo dimer studied by single crystal W-band EPR.

Detailed knowledge of the type and strength of pair interactions between high-spin metal ions is paramount to the understanding and design of molecular magnetic materials. In this work, the anisotropic magnetic interactions in a beta-diketonate-alkoxide iron(III) dimer compound, [Fe2(OCH3)2(dbm)4, Hdbm=dibenzoylmethane] (Fe2) have been investigated by single crystal electron paramagnetic resonance (EPR) in the W-band (at 95GHz). The diamagnetic substitution method was employed using the isomorphous gallium(III)-based compound doped with iron(III) to produce Ga-Fe dimers (GaFe). The single-ion zero-field splitting (ZFS) tensor could be separately determined in GaFe with the iron ion in a local environment quasi-identical to the one in Fe2. Its principal directions are found to point in arbitrary directions, uncorrelated with the Fe-O bonds. The Fe2 EPR spectra consist of transitions within the lowest multiplet states S=1,2,3, which were analyzed using the full spin Hamiltonian description of an exchange coupled pair of s=5/2 spins. The anisotropic spin-spin interaction tensor of Fe2 possesses a principal axis close to the Fe-Fe direction and was shown to arise both from through-space (dipolar) and through-bond (anisotropic exchange) contributions. The latter involves an rhombic component JE=(JX-JY)/2 approximately 0.093 cm-1 of magnitude comparable to the dipolar interaction, and even to the rhombic part of the single-ion ZFS (E=0.097 cm-1). Our results show that the anisotropic exchange, usually neglected for S-type ions, is significant for the anisotropic interactions in exchange-coupled iron(III) clusters, including the Fe4 and Fe8 families of single-molecule magnets and the antiferromagnetic iron wheels.

The use of tropical bromeliads (Tillandsia spp.) for monitoring atmospheric pollution in the town of Florence, Italy.

The results of an experiment with two species of epiphytic angiosperms (Tillandsia caput-medusae and T. bulbosa) for monitoring polycyclic aromatic hydrocarbons (PAHs) in the air of Florence, Italy, are presented. PAHs are compounds known to be dangerous because of their carcinogenic potential, and among cormophytes, tillands (monocotyledons equipped with peculiar, specialised, epidermal trichomes) are considered promising for air pollution biomonitoring. PAHs data were obtained using GC/MS analysis of plant extracts. Analytical data indicated an increasing trend in time of PAHs bioaccumulation. This result was compared with instrumentally recorded parameters such as meteorological (rain) and environmental ones (PM10), indicating that trichome-operated physical capture of aerial particles was prominent in PAHs bioaccumulation on tillands. SEM (scanning electron microscope) observations confirmed the role of the trichomes. This work indicates that tillands are particularly useful, low-cost biomonitoring organisms inside their area of distribution (all Latin American countries and southern USA) where these plants are easily available, but also wherever the climate allows them to survive.

The use of tropical bromeliads (Tillandsia spp. ) for monitoring atmospheric pollution in the town of Florence, Italy

The results of an experiment with two species of epiphytic angiosperms (Tillandsia caput-medusae and T. bulbosa) for monitoring polycyclic aromatic hydrocarbons (PAHs) in the air of Florence, Italy, are presented. PAHs are compounds known to be dangerous because of their carcinogenic potential, and among cormophytes, tillands (monocotyledons equipped with peculiar, specialised, epidermal trichomes) are considered promising for air pollution biomonitoring. PAHs data were obtained using GC/MS analysis of plant extracts. Analytical data indicated an increasing trend in time of PAHs bioaccumulation. This result was compared with instrumentally recorded parameters such as meteorological (rain) and environmental ones (PM10), indicating that trichome-operated physical capture of aerial particles was prominent in PAHs bioaccumulation on tillands. SEM (scanning electron microscope) observations confirmed the role of the trichomes. This work indicates that tillands are particularly useful, low-cost biomonitoring organisms inside their area of distribution (all Latin American countries and southern USA) where these plants are easily available, but also wherever the climate allows them to survive.

Structure and Magnetic Properties of a Dodecanuclear Twisted-Ring Iron(III) Cluster.

An unprecedented nonplanar structure characterizes the complex [Fe(OCH3 )2 (dbm)]12 (on the left in the picture), which contains the largest cyclic ferric cluster yet reported with chemically equivalent bridging units. It is made up of twelve high-spin, antiferromagnetically coupled iron(III) centers and neatly reacts with NaI or LiI templates in organic solution to give hexairon(III) coronates (right). Fe=•, O=○, NaI or LiI=• Hdbm=dibenzoylmethane.

Molecule-Based Magnets: Ferro- and Antiferromagnetic Interactions in Copper(II)-Polyorganosiloxanolate Clusters.

The magnetic behavior of the clusters [(PhSiO(2))(6)Cu(6)(O(2)SiPh)(6)].6EtOH (1), Na(4)[(PhSiO(2))(12)Cu(4)].8(n)()BuOH (2), and K(4)[(C(2)H(3)SiO(2))(12)Cu(4)].6(n)()BuOH (3) has been investigated by combined magnetic susceptibility measurements and variable-temperature EPR techniques (9.25 and 245 GHz). The six copper(II) ions in the core of 1, which approaches 6/mmm symmetry, are ferromagnetically coupled as a result of the geometry at the bridging siloxanolate oxygen atoms (Cu-O-Cu = 91.5-94.6 degrees; J = -42 cm(-)(1) with H = J S(i)().S(i)()(+1), S(7) = S(1)). The ground S = 3 spin state is split in zero field mainly due to anisotropic exchange contributions (D = 0.30 cm(-)(1)). Notably, both the magnitude and the sign of the zero-field splitting parameter have been determined from HF-EPR spectra. Large antiferromagnetic Cu-Cu interactions (J approximately 200 cm(-)(1)) and an S = 0 ground state have been detected in the tetranuclear clusters 2 and 3 as a consequence of the larger Cu-O-Cu angles. The results presented in the paper are relevant to the search for new molecule-based magnetic materials.