M. Manuela M. Raposo

2-Arylthienyl-Substituted 1,3-Benzothiazoles as New Nonlinear Optical Chromophores

A series of nonlinear optical chromophores 6 containing a substituted benzothiazole ring have been synthesized and characterized. 1,3-Benzothiazoles 6 were prepared by treating various formyl derivatives of thienyl compounds withortho-aminobenzenethiol in fair to excellent yields. These in turn were prepared by Suzuki coupling between aryl and thienyl precursors. The electronic interactions between donor and acceptor end groups in the conjugated 1,3-benzothiazoles 6 are revealed by the intense and markedly solvatochromic CT transitions. The solvatochromic behaviour of compounds 6 was determined by linear regression analyses of absorption maxima in several solvents, where benzothiazole 6f was found to be a very appropriate indicator dye whose absorption wavenumbers (Δmax = 1590 cm–1) in aliphatic and dipolar aprotic and in aromatic and chlorinated solvents correlated excellently with the π* values defined by Kamlet and Taft. Hyper-Rayleigh scattering was used to measure the first hyperpolarizabilities β of the aforementioned compounds. Thermogravimetric analysis (TGA) was used to evaluate their thermal stability. The experimental results indicate that good nonlinearity and thermal stability are well balanced for chromophores 6, making them good candidates for device applications. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Enhanced Functionality for Donor–Acceptor Oligothiophenes by means of Inclusion of BODIPY: Synthesis, Electrochemistry, Photophysics, and Model Chemistry

We have synthesized several new push-pull oligothiophenes based on the boron dipyrromethene (BODIPY) moiety as the electron acceptor and the more well-known oligothiophenes substituted with N,N-dialkylamino functions to enhance their electron-donor ability. A complete characterization of the electronic properties has been carried out; it consists of their photophysical, electrochemical, and vibrational properties. The compounds have been studied after chemical treatment with acids and after oxidation. In this regard, they can be termed as NIR dyes and amphoteric redox electroactive molecules. We have described the presence of dual fluorescence in these molecules and fluorescence quenching either by energy transfer or, in the push-pull molecules, by electron exchange. The combination of electrochemical and proton reversibility along with the interesting optical properties of the new species offer an interesting platform for sensor and material applications.

Synthesis and study of the use of heterocyclic thiosemicarbazones as signaling scaffolding for the recognition of anions.

A family of heterocyclic thiosemicarbazone dyes (1-9) linked to different furan, thiazole, (bi)thiophene, and arylthiophene pi-conjugated bridges were synthesized in good yields, and their response toward anions was studied. Acetonitrile solutions of 1-9 show bands in the 326-407 region that are modulated by the electron-donor or -acceptor strength of the heterocyclic systems appended to the phenylthiosemicarbazone moiety. Anions of different shape such as fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate, cyanide, and thiocyanate were employed for the recognition studies. From these anions, only fluoride, cyanide, acetate, and dihydrogen phosphate displayed sensing features. Two different effects were observed, (i) a low bathochromic shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the growth of a new red-shifted band with a concomitant change of the solution from yellow or pale yellow to orange-red due to deprotonation. The extent of each process is a balance between the acidity tendency of the thioureido-NH donors modulated by the donor or acceptor groups in the structure of the receptors and the basicity of the anions. Fluorescence studies were also in agreement with the different effects observed on the UV/vis titrations. Stability constants for the two processes (complex formation + deprotonation) for selected receptors and the anions fluoride and acetate were determined spectrophotometrically using the program HYPERQUAD. Semiempirical calculations to evaluate the hydrogen-donating ability of the dyes and (1)H NMR titrations experiments with fluoride were carried out. A prospective electrochemical characterization of compound 3 in the presence of anions was also performed.

Formylation, dicyanovinylation and tricyanovinylation of 5-alkoxy- and 5-amino- substituted 2,2'-bithiophenes

Abstract Several donor–acceptor-substituted bithiophenes were synthesized by functionalization of the corresponding 5-alkoxy- or 5-aminobithiophenes 1 by different methods: Vilsmeier formylation, metalation followed by reaction with DMF, direct tricyanovinylation reaction using TCNE or Knoevenagel condensation starting from the corresponding 5-formyl- derivatives of 1 .

Synthesis, Characterization and Metal Ion Detection of Novel Fluoroionophores Based on Heterocyclic Substituted Alanines

The synthesis of new fluorescent probes containing the thiophene and benzoxazole moieties combined with an alanine residue is described. The resulting highly fluorescent heterocyclic alanine derivatives respond via a quenching effect, with paramagnetic Cu(II) and Ni(II) metal ions and with diamagnetic Hg(II), as shown by the absorption and steady-state fluorescence spectroscopy studies. The formation of mononuclear or dinuclear metal complexes was postulated based on the presence of the free carboxylic acid as binding site and also with the interaction with the donor atoms in the chromophore. Interaction with other important biological metal ions such as Zn(II), Ca(II) and Na(I) was also explored.

Bioinspired Systems for Metal-Ion Sensing: New Emissive Peptide Probes Based on Benzo(d)oxazole Derivatives and Their Gold and Silica Nanoparticles )

Seven new bioinspired chemosensors (2-4 and 7-10) based on fluorescent peptides were synthesized and characterized by elemental analysis, (1)H and (13)C NMR, melting point, matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and IR and UV-vis absorption and emission spectroscopy. The interaction with transition- and post-transition-metal ions (Cu(2+), Ni(2+), Ag(+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Fe(3+)) has been explored by absorption and fluorescence emission spectroscopy and MALDI-TOF-MS. The reported fluorescent peptide systems, introducing biological molecules in the skeleton of the probes, enhance their sensitivity and confer them strong potential for applications in biological fields. Gold and silica nanoparticles functionalized with these peptides were also obtained. All nanoparticles were characterized by dynamic light scattering, transmission electron microscopy, and UV-vis absorption and fluorescence spectroscopy. Stable gold nanoparticles (diameter 2-10 nm) bearing ligands 1 and 4 were obtained by common reductive synthesis. Commercial silica nanoparticles were decorated at their surface using compounds 8-10, linked through a silane spacer. The same chemosensors were also taken into aqueous solutions through their dispersion in the outer layer of silica core/poly(ethylene glycol) shell nanoparticles. In both cases, these complex nanoarchitectures behaved as new sensitive materials for Ag(+) and Hg(2+) in water. The possibility of using these species in this solvent is particularly valuable because the impact on human health of heavy- and transition-metal-ion pollution is very severe, and all analytical and diagnostics investigations involve a water environment.

The morphology of layer-by-layer films of polymer/polyelectrolyte studied by atomic force microscopy

Layer-by-layer (LBL) films of a semiconducting polymer (POMA) alternated with a polyelectrolyte (PVS), adsorbed onto silicon oxide, mica, ITO/glass, Au/Cr/glass, hydrophilic and hydrophobic glass were studied by atomic force microscopy (AFM). The samples were characterized LBL with the AFM operating in the contact, friction and tapping modes, which allowed us to determine their morphological surface properties such as roughness, mean grain size, grain boundaries and power spectrum density. Their film thickness was measured by AFM using the tip as a scraping tool. Surface roughness increases with the number of bilayers until a constant value is reached. This is in agreement with the observed increase in the adsorbed amount (per layer) of POMA as the number of bilayers is increased, which also saturates after several bilayers. It is shown that the 3D growth behaviour indicates a similar microscopic mechanism for all systems under study, pointing to a stochastic growth process of the Eden model type, but strongly influenced by initial roughness and water affinity of the virgin substrates. The crystalline or amorphous nature of the substrates does not seem to influence the growth process.

Synthesis and evaluation of thiosemicarbazones functionalized with furyl moieties as new chemosensors for anion recognition

A family of heterocyclic thiosemicarbazone dyes (3a-f and 4) containing furyl groups was synthesized in good yields, characterized and their response in acetonitrile in the presence of selected anions was studied. Acetonitrile solutions of 3a-f and 4 showed absorption bands in the 335-396 nm range which are modulated by the electron donor or acceptor strength of the heterocyclic systems appended to the thiosemicarbazone moiety. Fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulphate, nitrate, acetate and cyanide anions were used in recognition studies. From these anions, only sensing features were seen for fluoride, cyanide, acetate and dihydrogen phosphate. Two clearly different chromo-fluorogenic behaviours were observed: (i) a small shift of the absorption band due to the coordination of the anions with the thiourea protons and (ii) the appearance of a new red shifted band due to deprotonation. For the latter effect, a change in the colour of solution from pale yellow to purple was observed. Fluorescence studies were also in agreement with the different effects observed in the UV/Vis titrations. In this case, hydrogen bonding interactions were visible through the enhancement of the emission band, whereas deprotonation induced the appearance of a new red-shifted emission. Logarithms of stability constants for the two processes (complex formation + deprotonation) for receptors in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec V1.1.18 program. Semi-empirical calculations to evaluate the hydrogen-donating ability of the receptors and a prospective electrochemical characterization of compound in the presence of fluoride were also performed.

Imidazoanthraquinone derivatives for the chromofluorogenic sensing of basic anions and trivalent metal cations.

Four imidazoanthraquinone derivatives (2a-d) were synthesized and characterized and their coordination behavior against selected anions and cations tested. Acetonitrile solutions of probes showed charge-transfer absorptions in the 407-465 nm range. The four probes emitted in the 533-571 nm interval. The recognition ability of 2a-d was evaluated in the presence of F(-), Cl(-), Br(-), I(-), OCN(-), BzO(-), ClO4(-), AcO(-), HSO4(-), H2PO4(-), and CN(-). Only F(-), AcO(-), and H2PO4(-) induced a new red-shifted absorption band that was attributed to a deprotonation process involving the amine moiety of the imidazole ring. Moreover, upon increasing quantities of F(-), AcO(-), and H2PO4(-), moderate quenching was induced in the emission of 2a-d together with the appearance of a new red-shifted band. The UV-visible and emission behavior of the four probes in the presence of Cu(2+), Co(2+), Mg(2+), Fe(3+), Ba(2+), Fe(2+), Ni(2+), Ca(2+), Zn(2+), Pb(2+), Cd(2+), Cr(3+), Al(3+), K(+), and Li(+) was also assessed. Only addition of Fe(3+), Cr(3+), and Al(3+) caused a new blue-shifted band in 2a-d that was ascribed to a preferential coordination with the acceptor part of the probes. Moreover, an important quenching of the emission was observed which was ascribed to the interaction between these trivalent cations and 2a-d.

Non‐Equilibrium Adsorbed Polymer Layers via Hydrogen Bonding

The layer-by-layer or self-assembly (SA) technique, based on the electrostatic interaction between oppositely charged layers, provides a simple and elegant way of producing multilayer structures from a variety of materials. Multilayers are normally employed because one layer is usually too thin for any device application. We show that considerably thicker layers may be obtained if the adsorption process is non-self-limiting, unlike the case of mechanisms entirely based on electrostatic attraction. This was obtained in spontaneously adsorbed layers of polyaniline (PANi), poly(o-methoxyaniline) (POMA) and tetrahydrothiophenium polyphenylenevinylidene, a PPV precursor. The non-self-limiting adsorption is attributed to H-bonding which is more effective for uncharged polymers. It is also shown that the adsorption process is only non-self-limiting under appropriate experimental conditions, since adsorption must be performed under a non-equilibrium condition. Producing thicker layers via the non-self-limiting adsorption procedure may have important implications in device applications, but for that one needs to overcome the drawback caused by aggregation that affects film quality. For PANi and POMA, we have also demonstrated that multilayers can still be produced from uncharged polymers, simply by protonating them in an acid solution, and then alternating one of them with a polyanion.