High-molecular-weight, soluble and thermostable alkoxy-substituted arylene−ethynylene/arylene−vinylene conjugated polymers, 13 and 14, have been successfully synthesized through the Horner−Wadsworth−Emmons olefination of luminophoric dialdehydes 7 and 9 and bisphosphonate 12 in very good yields. They were characterized through 1H NMR, 13C NMR, IR, and elemental analysis. The investigation of their photophysical and electrochemical properties has been carried out. Although almost identical absorption and emission spectra were obtained in dilute chloroform solution for all polymers 13, the full width at half-maximum (fwhm) value of the emission curves depends on the length of the attached side chains. The presence of anthracenylene units in 14 leads to a red shift of its absorption and emission spectra relative to 13. Strong self-reabsorption after excitation in solution was observed for this polymer. The solid-state photophysical properties of 13 and 14 (photoconductivity, absorption and emission spectra, fluorescence quantum yield, Stokes shift, and fwhm) greatly depend on the nature (linear or branched), length, and location of the grafted alkoxy side groups. Photoconductivity is easily detected in polymers having octadecyloxy chains (13aa, 13ab, 14). Long linear (octadecyl, i.e., 13aa) or short branched (2-ethylhexyl, i.e., 13 cc) side chains at position R2 (phenylene−vinylene segment) are necessary to obtain sharp and well-resolved emission spectra accompanied by high fluorescence quantum yields. The quasi-donor (phenylene−vinylene segment)−acceptor (arylene−ethynylene segment) nature of these polymers could explain the great discrepancy between the electrochemical band gap energy, E g ec ≈ 1.60 eV, as obtained from the onset values of the redox potentials in cyclic voltammetry and in differential pulse polarography measurements, and the optical band gap energy, E g opt ≈ 2.30 eV, from the absorption spectra.

Wave-guided thin-film distributed-feedback (DFB) polymer lasers are fabricated by spin coating a PPV-derived semiconducting polymer, thianthrene-DOO-PPV, onto oxidised silicon wafers with corrugated second-order periodic gratings. The gratings are written by reactive ion beam etching. Laser action is achieved by transverse pumping with picosecond laser pulses (wavelength 347.15 nm, duration 35 ps). The DFB-laser surface emission and edge emission are analysed. Outside the grating region the polymer film is used for comparative wave-guided travelling wave laser (amplified spontaneous emission (ASE)) studies. The pump pulse threshold energy density for wave-guided DFB-laser action (4-9 µJ cm-2) is found to be approximately a factor of two lower than the threshold for wave-guided travelling wave laser action. The spectral width of the DFB laser (down to DFB\approx0.07 nm) is considerably narrower than that of the travelling wave laser (TWL\approx14 nm). The DFB-laser emission is highly linearly polarised transverse to the grating axis (TE mode). Only at high pump pulse energy densities does an additional weak TM mode build up. The surface-emitted DFB-laser radiation has a low divergence along the grating direction. For both the DFB lasers and the travelling wave lasers, gain saturation occurs at high excitation energy densities

Alkoxy-substituted phenylene-ethynylene (PE)/phenylene-vinylene (PV) hybrid polymers of general constitutional structure (-Ar-CtC-Ar-CHdCH-) n (2), (-Ar-CtC-Ar-CHdCH-Ar-CtC-)n (3), and (-Ar-CtC-Ar-CtC-Ar-CHdCH-Ar-CHdCH-)n (4) have been synthesized and characterized. Comparisons of their photophysical properties in solution as well as in solid state (photoconductivity, absorption, emission, and electroluminescence) with those of their corresponding alkoxy-substituted poly(phenylene-ethynylene) (1) and poly(phenylene-vinylene) (5) have been carried out. Large octadecyloxy groups were selected as side chains in order to reduce the effect of π-π stacking interaction on the properties of the polymers in the solid state. This resulted in easy detection of photoconductivity and higher fluorescence quantum yields in solid state. The hybrid conjugation pattern in 4 is more favorable for photoconductivity than that in 2. A red shift of the absorption and emission spectra in solution is observed from 1 over 2b, 3, and 4 to 5. LED devices of ITO/PEDOT/polymer/Ca configuration have been fabricated with all compounds, except 2a. The phenylvinylene side groups in 3 not only give rise to a red shift of the solid-state photoluminescence spectrum and electroluminescence spectrum (relative to 2b) but also bring about a decrease of the turn-on voltage and improve the electroluminescence efficiency for more than 100 times.

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A benzoin-derived diol linker was synthesized and used to generate biocompatible polyesters that can be fully decomposed on demand upon UV irradiation. Extensive structural optimization of the linker unit was performed to enable the defined encapsulation of diverse organic compounds in the polymeric structures and allow for a well-controllable polymer cleavage process. Selective tracking of the release kinetics of encapsulated model compounds from the polymeric nano- and microparticle containers was performed by confocal laser scanning microscopy in a proof-of-principle study. The physicochemical properties of the incorporated and released model compounds ranged from fully hydrophilic to fully hydrophobic. The demonstrated biocompatibility of the utilized polyesters and degradation products enables their use in advanced applications, for example, for the smart packaging of UV-sensitive pharmaceuticals, nutritional components, or even in the area of spatially selective self-healing processes.

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Inkjet printing was used for the preparation of ternary polymer/polymer/fullerene layers for organic solar cell application, as part of a combinatorial setup for the preparation and characterization of thin-film libraries. Poly(phenylene-ethynylene)-alt-poly(phenylene-vinylene) (PPE-alt-PPV) and poly(diketopyrrolopyrrole-alt-fluorene) (P(DPP-alt-F)) were systematically blended with poly(3-octylthiophene) (P3OT) and investigated by UV-vis spectroscopy to improve the photon harvesting by extending the absorption range. The blends with the broadest absorption range (20 and 40 wt % of PPE-alt-PPV and P(DPP-alt-F), respectively) were mixed with mono(1-[3-(methoxycarbonyl)propyl]-1-phenyl)-[6,6]C61 (PCBM). The blend with the low band gap polymer P(DPP-alt-F) revealed the most extended absorption, which ranges over the whole visible spectrum (350 to 750 nm). The mixing with PCBM (ratio 1/3) led to an optimal emission quenching and revealed a smooth film formation. In this contribution, we show that the combinatorial screening using inkjet printing represents an effective, time- and material-saving workflow for the investigation of polymer blend libraries, which is of high interest for the development of new materials for active layers in organic photovoltaics.