The effects of alkyl substitution on the aggregation of π-conjugated dyes: spectroscopic study and modelling.

A family of dithienosilole-based dyes with alternating donor and acceptor conjugated groups, decorated with linear or branched alkyl chains at different positions on the backbone, have been obtained and investigated in different aggregation states. These dyes are characterized by almost panchromatic absorption and by near-IR emission, with good quantum yields in a variety of solvents with different polarity. We demonstrate that the nature and position of the alkyl substituents strongly govern the self-assembly of the dyes, whose packing is also sensitive to external stimuli, such as grinding and water addition. Thanks to computational results and theoretical modelling, we are able to interpret the results based on two possible preferential packings, characterized by distinct spectroscopic behaviour, whose abundance can be tuned according to the nature and position of the alkyl chains, as well as via external stimuli.

First Class of Phosphorus Dendritic Compounds Containing ß-Cyclodextrin Units in the Periphery Prepared by CuAAC.

A new class of phosphorus dendritic compounds (PDCs) having a cyclotriphosphazene (P3N3) core and decorated with six ß-cyclodextrin (ßCD) units, named P3N3-[O-C6H4-O-(CH2)n-ßCD]6, where n = 3 or 4 was designed, and the synthesis was performed using copper (I) catalyzed alkyne-azide cycloaddition (CuAAC). To obtain the complete substitution of the P3N3, two linkers consisting of an aromatic ring and an aliphatic chain of two different lengths were assessed. We found that, with both linkers, the total modification of the periphery was achieved. The two new obtained dendritic compounds presented a considerably high water solubility (>1 g/mL). The compounds comprised in this new class of PDCs are potential drug carrier candidates, since the conjugation of the ßCD units to the P3N3 core through the primary face will not only serve as surface cover but, also, provide them the faculty to encapsulate various drugs inside the ßCDs cavities.

Fluorescent phosphorus dendrimers excited by two photons: synthesis, two-photon absorption properties and biological uses.

Different types of two-photon absorbing (TPA) fluorophores have been synthesized and specifically functionalized to be incorporated in the structure of phosphorus dendrimers (highly branched macromolecules). The TPA fluorophores were included in the periphery as terminal functions, in the core, or in the branches of the dendrimer structures, respectively. Also the functionalization in two compartments (core and surface, or branches and surface) was achieved. The consequences of the location of the fluorophores on the fluorescence and TPA properties have been studied. Several of these TPA fluorescent dendrimers have water-solubilizing functions as terminal groups, and fluorophores at the core or in the branches. They have been used as fluorescent tools in biology for different purposes, such as tracers for imaging blood vessels of living animals, for determining the phenotype of cells, for deciphering the mechanism of action of anticancer compounds, and for safer photodynamic therapy.

π-Stacking Interactions of Graphene-Coated Cobalt Magnetic Nanoparticles with Pyrene-Tagged Dendritic Poly(Vinylidene Fluoride).

This study investigates the non-covalent coating of cobalt magnetic nanoparticles (MNPs) involving a graphene surface with pyrene-tagged dendritic poly(vinylidene fluoride) (PVDF). Dendrimers bearing a pyrene moiety were selected to play the role of spacers between the graphene surface of the MNPs and the PVDF chains, the pyrene unit being expected to interact with the surface of the MNPs. The pyrene-tagged dendritic spacer 11 decorated with ten acetylenic units was prepared and fully characterized. Azido-functionalized PVDF chains were then grafted onto each branch of the dendrimer using Huisgen's [3+2] cycloaddition reaction. Next, the association of the resulting pyrene-tagged dendritic PVDF 13 with commercially available Co/C MNPs by π-stacking interactions was studied by fluorescence spectroscopy. Evaluated were the stability of the π-stacking interactions when the temperature increased and the reversibility of the process when the temperature decreased. Also, hybrid MNPs were prepared from pyrene-tagged dendrimers decorated either with acetylenic functions (11) or with PVDF branches (13), and they were characterized by transmission electron microscopy and comparative elemental analysis was carried out with naked MNPs.

Synthesis and Characterization of Novel Polythiophenes Containing Pyrene Chromophores: Thermal, Optical and Electrochemical Properties.

A novel series of pyrene containing thiophene monomers TPM1-5 were synthesized and fully characterized by FTIR, MS, ¹H- and (13)C-NMR spectroscopy; their thermal properties were determined by TGA and DSC. These monomers were chemically polymerized using FeCl3 as oxidizing agent to give the corresponding oligomers TPO1-5) and they were electrochemically polymerized to obtain the corresponding polymer films deposited onto ITO. All oligomers exhibited good thermal stability, with T10 values between 255 and 299 °C, and Tg values varying from 36 to 39 °C. The monomers showed an absorption band at 345 nm due to the S0 → S2 transition of the pyrene group, whereas the fluorescence spectra showed a broad emission band arising from the "monomer" emission at 375-420 nm. The obtained polymers exhibited two absorption bands at 244 and 354 nm, due to the polythiophene and the pyrene moieties, respectively. The fluorescence spectra of polymers showed a broad "monomer" emission at 380-420 nm followed by an intense excimer emission band at 570 nm, due to the presence of intramolecular pyrene-pyrene interactions in these compounds.