Helicene Appended Benzothiadiazoles as Chiral Emitters.

A homologous series of 4,7-bis(aryl) substituted benzothiadiazole (BTD) compounds, containing the helicenic derivatives bis([4]helicene), bis([5]helicene) and bis([6]helicene), have been prepared upon a double Suzuki coupling between 3,6-bis(pinacolyl-borane)-BTD and the corresponding bromo-aryl precursors. The single crystal X-ray structure of the bis([4]helicene) compound shows the existence of both helicities (M) and (P) on the same molecule. All the compounds of the series are highly emissive in solution, with quantum yields of the emission ranging from 50 to 91%. The enantiopure compounds (M,M) and (P,P) for the BTD-bis([6]helicene) have been prepared from the corresponding enantiopure 2-bromo-[6]helicene precursors. Their chiroptical properties have been investigated in correlation with density functional theory (DFT) calculations, which allowed to confidently assign the absolute configuration of the helicene arms and to characterize the different electronic transitions, including the low energy charge transfer excitation from helicenes to BTD. The enantiomerically pure fluorophores (M,M)- and (P,P)-BTD-bis([6]helicene), which exist in solution as two main conformers, according to the DFT calculations, show CPL activity in solution, with glum factors of ≈ 1.7×10-3 at lem = 525 nm, and also in the solid state, with glum factors of ≈ 1.2×10-3 in spite of the strong decrease of the quantum efficiency.

Tuning the photophysical and chiroptical properties of [4]helicene-diketopyrrolopyrroles.

Synthesis and functionalization of diketopyrrolo[3,4-c]pyrrole (DPP) derivatives containing chiral groups able to induce a strong chiral perturbation of the DPP core are still a challenging task. We report in this work the straightforward preparation of four bis([4]helicene)-DPP and bis([4]thiahelicene)-DPP dyes upon the condensation of 2-CN-[4](thia)helicene precursors, followed by their N-alkylation by nucleophilic substitution (compounds 9-11) or by a Mitsunobu-type strategy (compound 12). Compound 12, which contains sec-phenylethyl groups attached to the nitrogen atoms, has been obtained as (R,R) and (S,S) enantiomers. The four DPP-helicenes are luminescent in solution, while the N-benzyl (10) and N-sec-phenethyl (12) are emissive in the solid state as well. The chiroptical properties of compound 12 in solution and in the solid state indicate a strong chiral perturbation provided by the α-stereogenic centres, in spite of the stereodynamic nature of the [4]helicene flanking units.

Straightforward N-alkylation of diketopyrrolopyrroles through the Mitsunobu reaction with benzyl, α-branched, and chiral alcohols.

The N-alkylation of diketopyrrolopyrroles (DPPs) represents a fundamental step to ensure solubility and further processability. Commonly used nucleophilic substitution in halogenated derivatives is replaced in this work by the Mitsunobu reaction affording unprecedented DPPs with α-branched and chiral chains.

Thiophene-Bipyridine Appended Diketopyrrolopyrrole Ligands and Platinum(II) Complexes.

Straightforward palladium(II) catalyzed direct cross-coupling reaction between decyl, (S)-2-methyl-butyl, and dodecyl N-substituted diketopyrrolopyrrole thiophene (DPPT), including a 3-methoxy-thiophene derivative, and 6-bromo-2,2'-bipyridine afforded a series of mono- and bis-bipyridine substituted DPPT ligands 1-3. Complexation reactions with PtCl2(DMSO)2 provided ortho-metalated platinum(II) complexes 1-Pt and 2-Pt, together with the N^N^O complex 3d-Pt(N^N^O) resulted from the O-Me activation of the intermediary complex 3d-Pt(N^N). The ligand 1b and the mononuclear complexes 1a-Pt and 1b-Pt have been structurally characterized by single crystal X-ray structure, evidencing the establishment of numerous intermolecular π-π interactions in the solid state. Moreover, in the crystal structure of the model complex DMTB-Pt(N^N^O) (DMTB = 3,4-dimethoxy-(2,2'-bipyridine)) the chelating tridentate N^N^O mode is clearly evidenced. The chiral ligand 1b and its mononuclear complex 1b-Pt do not show any CD signal in solution, but they are CD active in the solid state with bisignate bands in the low energy region, opposite in sign between the ligand and the complex, suggesting helical supramolecular arrangement of the dpp chromophore in the solid state. Photophysical investigations demonstrate that all of the ligands are fluorescent with high quantum yields, while the emission is quenched for the complexes, except partially in 3d-Pt(N^N), very likely through an intersystem crossing mechanism promoted by the heavy metal. Density functional theory calculations support the differences observed between the absorption properties of the ligands, ortho- and non-ortho-metalated complexes. The highly fluorescent bipyridine ligands reported herein open the way toward multifunctional transition metal complexes and their use in organic electronics.

Ligand exchange reactions on the chiral Au38 cluster: CD modulation caused by the modification of the ligand shell composition.

Ligand exchange reactions have become a highly versatile post-synthetic strategy to accurately engineer the ligand shell of atomically precise noble metal nanoclusters. Modifying the chemical structure of the exchanging ligand with chromophore substituents or adding chiral centers allow direct functionalization of the cluster with desired properties. As such, post-functionalized gold nanoclusters with unique physicochemical properties find applications in optoelectronics, catalysis and biomedicine. Herein, we successfully carried out ligand exchange reactions between the chiral Au38(2-PET)24 cluster (both racemic and enantiopure forms) and the helically chiral but configurationally labile 2-thio[4]helicene ligand (TH4). The reaction products with a composition of Au38(2-PET)24-x(TH4)x were analyzed using UV-vis spectroscopy and MALDI mass spectrometry. It was found that up to ten 2-PET ligands can be replaced with the helicene ligand on the cluster surface according to MALDI analysis. Consequently, the UV-vis and CD spectra of the cluster have been strongly affected by the ligand exchange reaction. The intensities of the CD signals of Au38(2-PET)24-x(TH4)x were drastically reduced and red shifted with respect to the reference Au38(2-PET)24 cluster. Moreover, the appearance of the other enantiomer in the HPLC chromatogram revealed the partial racemization of the cluster. DFT calculations were performed and they support the experimental observations and show that the observed chiroptical changes in UV-vis and CD spectra are exchange-site dependent. The calculations also demonstrate that charge transfer (CT) transitions occur between the Au38 cluster and the helicene ligand. Thus the ligand is directly involved in these transitions and contributes to the electronic states comprising those transitions.

Innovative Technologies for Cultural Heritage. Tattoo Sensors and AI: The New Life of Cultural Assets.

Conservation and restoration of cultural heritage is something more than a simple process of maintaining the existing. It is an integral part of the improvement of the cultural asset. The social context around the restoration shapes the specific actions. Today, preservation, restoration, enhancement of cultural heritage are increasingly a multidisciplinary science, meeting point of researchers coming from heterogeneous study areas. Data scientists and Information technology (IT) specialists are increasingly important. In this context, networks of a new generation of smart sensors integrated with data mining and artificial intelligence play a crucial role and aim to become the new skin of cultural assets.

Smart Portable Devices Suitable for Cultural Heritage: A Review.

This article reviews recent portable sensor technologies to apply in the Cultural Heritage (CH) fields. The review has been prepared in the form of a retrospective description of the sensor's history and technological evolution, having: new nanomaterials for transducers, miniaturized, portable and integrated sensors, the wireless transmission of the analytical signals, ICT_Information Communication Technology and IoT_Internet of Things to apply to the cultural heritage field. In addition, a new trend of movable tattoo sensors devices is discussed, referred to in situ analysis, which is especially important when scientists are in the presence of un-movable and un-tangible Cultural Heritage and Art Work objects. The new proposed portable contact sensors (directly applied to art work objects and surfaces) are non-invasive and non-destructive to the different materials and surfaces of which cultural heritage is composed.

Metal Free Graphene Oxide (GO) Nanosheets and Pristine-Single Wall Carbon Nanotubes (p-SWCNTs) Biocompatibility Investigation: A Comparative Study in Different Human Cell Lines.

The in vitro biocompatibility of Graphene Oxide (GO) nanosheets, which were obtained by the electrochemical exfoliation of graphite electrodes in an electrolytic bath containing salts, was compared with the pristine Single Wall Carbon Nanotubes (p-SWCNTs) under the same experimental conditions in different human cell lines. The cells were treated with different concentrations of GO and SWCNTs for up to 48 h. GO did not induce any significant morphological or functional modifications (demonstrating a high biocompatibility), while SWNCTs were toxic at any concentration used after a few hours of treatment. The cell viability or cytotoxicity were detected by the trypan blue assay and the lactate dehydrogenase LDH quantitative enzymatic test. The Confocal Laser Scanning Microscopy (CLSM) and transmission electron microscopy (TEM) analysis demonstrated the uptake and internalization of GO sheets into cells, which was localized mainly in the cytoplasm. Different results were observed in the same cell lines treated with p-SWCNTs. TEM and CLSM (Confocal Laser Scanning Microscopy) showed that the p-SWCNTs induced vacuolization in the cytoplasm, disruption of cellular architecture and damage to the nuclei. The most important result of this study is our finding of a higher GO biocompatibility compared to the p-SWCNTs in the same cell lines. This means that GO nanosheets, which are obtained by the electrochemical exfoliation of a graphite-based electrode (carried out in saline solutions or other physiological working media) could represent an eligible nanocarrier for drug delivery, gene transfection and molecular cell imaging tests.

Newly Developed Nano-Calcium Carbonate and Nano-Calcium Propanoate for the Deacidification of Library and Archival Materials.

Paper-based cultural heritage objects are subject to natural deterioration due to internal and external factors, that is, the presence of heavy metals, incorrect conservation, humidity, exposure of the artifacts to pollutants, light, and high temperatures. To contrast the decay of the original objects, it is necessary to study and apply innovative specific techniques, set up novel preservation methodologies, and implement or synthesize new products. As the nanomaterial science field developed over the last decades, the usage of nanomaterials in cultural heritage gained a prominent role. Such an excitement for the novel materials opened the path for an uncontrolled transfer of nanoparticles developed for different applications to paper restoration, neglecting all their possible interactions with the support or the graphic media. The aim of this work was to synthesize new nanomaterials expressly conceived for the treatment of library materials. To evaluate their possible insertion in the official conservation treatments that are subjected to validation by Istituto Centrale Restauro e Conservazione Patrimonio Archivistico e Librario, the new nanomaterials were tested both on laboratory paper samples and on original documents. This work presents the results of these studies (some of which still preliminary) stressing the positive and extremely promising outcomes of this research.

Benchmarking DFT and semi-empirical methods for a reliable and cost-efficient computational screening of benzofulvene derivatives as donor materials for small-molecule organic solar cells.

A systematic computational investigation on the optical properties of a group of novel benzofulvene derivatives (Martinelli 2014 Org. Lett. 16 3424-7), proposed as possible donor materials in small molecule organic photovoltaic (smOPV) devices, is presented. A benchmark evaluation against experimental results on the accuracy of different exchange and correlation functionals and semi-empirical methods in predicting both reliable ground state equilibrium geometries and electronic absorption spectra is carried out. The benchmark of the geometry optimization level indicated that the best agreement with x-ray data is achieved by using the B3LYP functional. Concerning the optical gap prediction, we found that, among the employed functionals, MPW1K provides the most accurate excitation energies over the entire set of benzofulvenes. Similarly reliable results were also obtained for range-separated hybrid functionals (CAM-B3LYP and wB97XD) and for global hybrid methods incorporating a large amount of non-local exchange (M06-2X and M06-HF). Density functional theory (DFT) hybrids with a moderate (about 20-30%) extent of Hartree-Fock exchange (HFexc) (PBE0, B3LYP and M06) were also found to deliver HOMO-LUMO energy gaps which compare well with the experimental absorption maxima, thus representing a valuable alternative for a prompt and predictive estimation of the optical gap. The possibility of using completely semi-empirical approaches (AM1/ZINDO) is also discussed.

Synthesis and structure of conjugated molecules with the benzofulvene core.

A general method to synthesize conjugated molecules with a benzofulvene core is reported. Up to four conjugated substituents have been introduced via a three-step sequence including (1) synthesis of 1,2-bis(arylethynyl)benzenes; (2) exo-dig electrophilic cyclization promoted by iodine; and (3) cross-coupling reaction of the resulting bis-iodobenzofulvenes with organoboron, organotin, or ethynyl derivatives under Pd catalysis. Structural aspects of the new compounds are discussed.