Tetra- and tri-thienyl ethenes: new fluorescent photochromic compounds.

In this work the photochemistry and photophysics of two new ethenic compounds, a tetra-thienylethene (tetrakis) and a tri-thienylethene (triakis), have been investigated by steady state and time-resolved UV-vis absorption and luminescence spectroscopies. The quantum yields of the UV-photoinduced ring-closure reaction (Φ(O→C)) and of the visible-stimulated cycloreversion reaction (Φ(C→O)) were determined as a function of the temperature in 3-methylpentane. The trends of Φ(O→C) and Φ(C→O) with temperature suggest that a barrier exists to the ring opening reaction which hampers the cycloreversion in a rigid matrix at 80 K. For the closure reaction, a negative effect of the temperature on Φ(O→C) reflects an increased concentration of the more easily isomerizable antiparallel conformer with decreasing the temperature. Quantum yields and lifetimes of fluorescence, observed for tetrakis in both the colourless and coloured forms and for triakis only for the coloured form, were determined. The solvent and temperature effects on fluorescence were investigated. Nanosecond time-resolved experiments showed the formation of a triplet transient from tetrakis which could be a precursor of the main reaction photoproduct. For triakis no transient was detected.

New thermally irreversible and fluorescent photochromic diarylethenes.

A photokinetic investigation is here carried out on four newly synthesized diarylethenes with the aim to test their performance as photoreversible chromogenic and light emitting materials. The pentatomic ring, which fixes these diarylethenes in the cis conformation, contains a Si atom or a PO group. The 1,2 positions at the ethenic bond are symmetrically substituted with thienyl or benzothienyl groups. The results are compared with those for the structurally related and widely studied 1,2-bis(2-methyl-benzo[b]thiophen-3-yl)perfluorocyclopentene (BTF6), investigated here under the same experimental conditions. Spectra of the colorless and colored forms and photoreaction quantum yields were determined; temperature, excitation wavelength and viscosity effects were explored. Compounds containing benzothienyl substituents were found to be good bistable photochromes, with high photochemical yields of both the cyclization and cycloreversion reactions, and to display appreciable fluorescence emission from the colored forms, which is a rare and desirable property for photochromes. In contrast, the molecules not bearing the benzene condensed rings were found unsuitable as photochromes because of side degradation processes occurring in competition with cyclization.

Transient absorption studies of the photochromic behavior of 3H-naphtho[2,1-b]pyrans linked to thiophene oligomers via an acetylenic junction.

The photophysical and photochemical properties of four 3,3-diphenyl-3H-naphtho[2,1- b]pyrans substituted, via an acetylenic junction, to (thiophene) n oligomers (n = 0-3 units) were investigated by transient absorption in the femtosecond to microsecond time domain and by stationary absorption and fluorescence. The decay of the initially produced excited S1(pi pi*) state is found to occur via three competing processes: fluorescence, intersystem crossing, and a ring-opening reaction leading to a colored merocyanine product, with relative yields varying drastically with n. Whereas ultrafast (sub-picosecond) reaction dynamics and high product quantum yield are observed for n = 0 and 1, the reaction is considerably slowed down on going to the n = 2 (105 ps) compound and does not occur for n = 3. A reaction scheme that accounts for this behavior is proposed and the effect of the oligothiophenic chain length on the photoinduced properties is discussed. It is suggested that increasing the chain length from 1 to 3 thiophene units stabilizes the S1(pi pi*) state by pi conjugation and induces an excited-state potential barrier along the reaction pathway.

Photoinduced processes in dipyrrolyl-perfluoro-cyclopentenes.

The photobehavior of five photochromic dipyrrolyl-perfluoro-cyclopentenes was studied by steady state and time-resolved absorption spectroscopy. The quantum yields of the UV-photoinduced ring-closing reaction (coloration) and the visible-stimulated cycloreversion reaction (bleaching) were measured. Kinetic and thermodynamic parameters of thermal bleaching were also determined. Nanosecond time-resolved experiments showed formation of a transient, which was not a precursor of the reaction photoproduct. This transient was tentatively assigned to a radical cation formed by direct photoionization through a short-lived triplet state. The nature of the transient species was supported by photoinduced electron transfer to electron acceptors.

Automated synthesis of new ferrocenyl-modified oligonucleotides: study of their properties in solution.

We have developed new ferrocenyl-modified oligonucleotide (ODN) probes for electrochemical DNA sensors. A monofunctional ferrocene containing phosphoramidite group has been prepared, and a new bisfunctional ferrocene containing phosphoramidite and dimethoxytrityl (DMT) groups has been developed. These ferrocenyl-phosphoramidites have been directly employed in an automated solid-phase DNA synthesizer using phosphoramidite chemistry. The advantages of this method are that it allows a non-specialist in nucleotide chemistry to access labeled ODNs and that it has demonstrated good results. ODNs modified at the 3' and/or 5' extremities have been prepared, with the incorporation of the ferrocenyl group into the chain. The 5' position appears to be more important due to its particular behavior. The thermal stability and electrochemical properties of these new ODN ferrocenes were analyzed before and after hybridization with different ODNs. The feasibility of using these new ferrocenyl-labeled ODNs in DNA sensors has been demonstrated.

Comprehensive photokinetic and NMR study of a biphotochromic supermolecule involving two naphthopyrans linked to a central thiophene unit through acetylenic bonds.

A photophysical and photochemical study of a biphotochromic compound where two naphthopyran units are linked by an acetylene-thiophene-acetylene bridge has been carried out in toluene. Both fluorescence and intersystem crossing to the triplet manifold were found to compete with the photocoloration process. Two photoproducts (transoid-trans and transoid-cis stereoisomers), absorbing at approximately 480 nm and corresponding to the opening of a single photochromic unit, were detected by spectrophotometric analysis after short irradiation time in diluted solution and identified by 1H-nuclear magnetic resonance (NMR) spectroscopy. After prolonged irradiation at 228 K of highly concentrated solutions (up to 3 x 10(-3) mol dm(-3)), two additional isomers, absorbing at approximately 550 nm, were formed. Their NMR spectra indicate the opening of both photochromic units. An interesting effect of selective vibronic excitation was found, showing that the photoreaction is favored at excited vibronic levels to the detriment of the radiative relaxation.

Supported synthesis of ferrocene modified oligonucleotides as new electroactive DNA probes.

The use of 1-[3-O-(2-cyanoethyl-N,N-diisopropylphosphor amidityl)propyl]ferrocene and 1-[3-O-dimethoxytrityl propyl]-1'-[3'-O-(2-cyanoethyl-N,N-diisopropylphosphoramidityl) propyl] ferrocene as reactive synthons for DNA/RNA synthesizer allows to generate ferrocene-labelled oligonucleotides with remarkable DNA detection properties.

Continuous irradiation and flash-photolysis studies of new[3H]naphtho[2,1-b]pyrans linked by covalent bonds to oligothiophene units. Effect of thiophene substituents on the photochromism.

The influence of oligothiophene substituents on five new [3H]naphtho[2,1-b]pyrans has been investigated using flash photolysis and continuous irradiation techniques. Photochromic properties strongly depend on the number and position of the thienyl units. Thienyl substitution increases the UV/visible absorbance of the lower energy transition of both the naphthopyran and merocyanine isomers. The rate constants of the thermal fading processes also increase with the number of thiophenic entities. Although several minor photoisomers, whose relative amounts depend on the irradiation conditions could be involved, it has been assumed that under continuous monochromatic irradiation, the evolution of the photochromic reaction can be described by the formation of only one photoisomer. Under these conditions, quantum yields of photocolouration and molar absorption coefficients of the non-isolable photomerocyanine isomer were evaluated by photokinetic analysis. Flash-photolytic colourability can be interpreted using continuous irradiation parameters. A linear correlation has been established between experimental and calculated colourability. This result shows that similar photochromic reactions leading to similar photoisomers are triggered either by polychromatic flash photolysis or by continuous monochromatic irradiation.

Effect of oligothiophene substituents on the photophysical and photochromic properties of a naphthopyran.

A spectrokinetic study of the photophysical and photochemical properties of a series of photochromes bearing thienyl (T(1)), dithienyl (T(2)) and terthienyl (T(3)) groups linked to a naphthopyran in position 3 (sp(3) carbon) or 8 (naphtho moiety) has been carried out. The effect of the number and position of the thienyl groups on the excited state properties of the six compounds in the singlet and triplet manifold has been investigated by stationary and pulsed fluorimetric techniques, laser flash photolysis and kinetic analysis of the colouration/decolouration processes upon continuous irradiation. On increasing the length of the oligothiophene moiety, the contribution of fluorescence to the deactivation processes becomes detectable, while the photocolouration yield decreases. Moreover, only for compounds with T(3) groups was the triplet absorption observed by laser flash photolysis; its decay did not contribute to photocolouration. The competition between physical (fluorescence emission and intersystem crossing) and chemical relaxations markedly affects the behaviour of the compound bearing the T(3) group at the naphtho moiety, which shows the most efficient intersystem crossing and fluorescence emission while does not lead to photoproduction of the coloured open form. A parallel study of the NMR spectra of the compounds bearing one thiophene group allowed two and four photomerocyanine-type photoproducts to be identified for the naphtho-substituted and pyran-substituted compounds, respectively. The compound with a thiophene group at the naphtho moiety was studied in more detail at different temperatures. On the basis of the combined optical and NMR spectrometric results, a reasonable mechanism of its photochromic behaviour is proposed.