Rosa Maria Ferreira Batista

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)

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.

Cyanide and fluoride colorimetric sensing by novel imidazo-anthraquinones functionalised with indole and carbazole

Novel imidazo-anthraquinones functionalised with indole and carbazole have been synthesised and characterised and their evaluation as colorimetric chemosensors was carried out in acetonitrile as well as in acetonitrile/H2O (97:3) in the presence of several anions such as F− , Cl− , Br− , I− , CN− , , , AcO− , BzO− , , , and . In addition, their behaviour in the presence of H+ and OH− was also studied. Upon addition of CN− and F− to acetonitrile solutions of compounds 1–3, a marked colour change from yellow to orange was observed and the fluorescence emission of 1 and 2 was switched ‘on’. The recognition in organic aqueous solution leads to the selective and sensitive naked-eye detection (mM) of CN− for all receptors, with an easily detectable colour change from yellow to orange. The binding stoichiometry between the receptors and the anions was found to be 2:1. The binding process was also followed by 1H NMR titrations showing that two different binding modes occurred in the presence of fluoride or cyanide anions, which is in agreement with the spectrophotometric titrations.

Triphenylamine–Benzimidazole Derivatives: Synthesis, Excited-State Characterization, and DFT Studies

The synthesis and comprehensive characterization of the excited states of four novel triphenylamine-benzimidazole derivatives has been undertaken in solution (ethanol and methylcyclohexane) at room temperature. This includes the determination of the absorption, fluorescence, and triplet-triplet absorption spectra, together with quantum yields of fluorescence, internal conversion, intersystem crossing, and singlet oxygen. From the overall data the radiative and radiationless rate constants could be obtained, and it is shown that the compounds are highly emissive with the radiative decay dominating, with more than 70% of the quanta loss through this deactivation channel. The basic structure of the triphenylamine-benzimidazole derivatives (1a) was modified at position 5 of the heterocyclic moiety with electron-donating (OH (1b), OCH3 (1c)) or electron-withdrawing groups (CN, (1d)). It was found that the photophysical properties remain basically unchanged with the different substitutions, although a marked Stokes shift was observed with 1d. The presence and nature of a charge-transfer transition is discussed with the help of theoretical (DFT and TDFT) data. All compounds displayed exceptionally high thermal stability (between 399 and 454 °C) as seen by thermogravimetric analysis.

The influence of the relative position of the thiophene and pyrrole rings in donor-acceptor thienylpyrrolyl benzothiazole derivatives. A photophysical and theoretical investigation

A detailed spectroscopic and photophysical study has been carried out on a series of heterocyclic compounds-known to display nonlinear optical properties-consisting on a electron donating thienylpyrrolyl pi-conjugated system functionalized with an electron acceptor benzothiazole moiety. The absorption, emission and triplet-triplet absorption together with all relevant quantum yields (fluorescence, intersystem crossing and internal conversion), excited state lifetimes and the overall set of deactivation rate constants (k(F), k(IC) and k(ISC)) were obtained in solution at room (293 K) and low (77 K) temperature. The optimized ground-state molecular geometries for the compounds together with the prediction of the lowest vertical one-electron excitation energy and the relevant molecular orbital contours for the compounds were also determined using density functional theory (DFT) at the B3LYP/3-21G* level. The experimental results showed that the photophysical properties are influenced by the relative position of the pyrrole and thiophene relative to the benzothiazole group.

Synthesis and characterization of the ground and excited states of tripodal-like oligothienyl-imidazoles.

Six new thiophene oligomers, here designated as tripodal-like oligothienyl-imidazoles, were synthesized and have been investigated in ethanol solution at room and low temperature. The oligomers bear a common core where two or more thiophenes are linked to one or more imidazole units that further links through its alpha-position to a different number of incremental thiophene units. The study involves a comprehensive spectral and photophysical investigation where the properties of the singlet and triplet states have been investigated regarding absorption, fluorescence and phosphorescence, transient triplet-triplet absorption together with all relevant quantum yields (fluorescence, phi(F), internal conversion, phi(IC), intersystem crossing, phi(T,) and singlet oxygen, phi(Delta)) and lifetimes. In addition, density functional theory quantum chemical calculations were performed to gain a detailed understanding of the molecular geometry and optical properties of the investigated oligomers. From the overall data, the radiative (k(F)) and radiationless (k(NR), k(IC), and k(ISC)) rate constants have been determined and it is shown that, in contrast with the parent oligothiophenes, the radiative competes with the radiationless deactivation channels. The results show that, by comparison with the oligothiophene counterparts, there is an augment of the relative contributions of the internal conversion and fluorescence processes relative to the S(1)~~-->T(1) intersystem crossing. Phosphosphorescence emission was found for the simplest member of the investigated compounds with a low quantum yield (phi(Ph) = 0.009) and a lifetime of 8 micros. The data also show that the introduction of a 4,5-dithienyl-imidazole moiety in a bi- or terthiophene oligomer results in, respectively, a 20-fold and a 3-fold increase of the fluorescence quantum yield relative to their oligothiophene counterparts. The synergy of the structural and photophysical properties, combined with the exceptional thermal stabilities, opens new perspectives related to the copolymerization of oligothiophenes with thienyl-imidazole units with potential application as organic light emitting devices.

New Fluorescent Heterocyclic Materials: Synthesis, Solvatochromic and Fluorescence Properties

Thienyl- and bithienyl-1,3-benzothiazoles 1 and 2 were synthesised by reacting various formyl thienyl and bithienyl derivatives with o-aminobenzenethiol in moderate to excellent yields. Evaluation of the solvatochromic and fluorescence properties of these compounds was carried out. Due to their strong fluorescence and also the strong push-pull character, benzothiazole derivatives 1 and 2 can be used as potential NLO materials or as fluorescent markers.

(Oligo)thienyl-imidazo-benzocrown ether derivatives : synthesis, photophysical studies and evaluation of their chemosensory properties

A series of novel (oligo)thienyl-imidazo-benzocrown ethers were synthesised through a simple method and evaluated as fluorimetric chemosensors for transition metal cations. Interaction with Ni(2+), Pd(2+), and Hg(2+) in ACN/DMSO solution (99:1) was studied by absorption and emission spectroscopy. Chemoselectivity studies in the presence of Na(+) were also carried out and a fluorescence enhancement upon chelation (CHEF) effect was observed following Hg(2+) complexation. Considering that most systems using fluorescence spectroscopy for detecting Hg(2+) are based on the complexation enhancement of the fluorescence quenching (CHEQ) effect, the present work represents one of the few examples for sensing of Hg(2+) based on a CHEF effect.

Synthesis and Characterization of New Push-Pull Anthraquinones Bearing an Arylthienyl-Imidazo Conjugation Pathway as Efficient Nonlinear Optical Chromophores

Compounds 1 were synthesized, in good to excellent yields (72-87%), through condensation of formyl-arylthiophene precursors 2 with 1,2-diaminoanthraquinone in ethanol at reflux, followed by cyclisation of the imine intermediate with Pb(OAc)4 in acetic acid at room temperature. Evaluation of the thermal, linear and NLO properties of these compounds was carried out. The  values of chromophores 1, measured by hyper-Rayleigh scattering (HRS) technique, are several times larger (49-67) than that of the standard reference molecule p-nitroaniline (pNA). Due to their excellent thermal stability, (Td = 341-446 oC), and good NLO properties, arylthienyl-imidazo-anthraquinones 1 could be used as new efficient and thermally stable NLO materials.