A family of soluble narrow band gap donor-acceptor conjugated polymers based on dioxythiophenes and cyanovinylenes is reported. The polymers were synthesized using Knoevenagel polycondensation or Yamamoto coupling polymerizations to yield polymers with molecular weights on the order of 10 000-20 000 g/mol, which possess solubility in common organic solvents. Thin film optical measurements revealed narrow band gaps of 1.5-1.8 eV, which gives the polymers a strong overlap of the solar spectrum. The energetic positions of the band edges were determined by cyclic voltammetry and differential pulse voltammetry and demonstrate that the polymers are both air stable and show a strong propensity for photoinduced charge transfer to fullerene acceptors. Such measurements also suggest that the polymers can be both p- and n-type doped, which is supported by spectroelectrochemical results. These polymers have been investigated as electron donors in photovoltaic devices in combination with PCBM ([6,6]-phenyl C(61)-butyric acid methyl ester) as an electron acceptor based on the near ideal band structures designed into the polymers. Efficiencies as high as 0.2% (AM1.5) with short circuit current densities as high as 1.2-1.3 mA/cm(2) have been observed in polymer/PCBM (1:4 by weight) devices and external quantum efficiencies of more than 10% have been observed at wavelengths longer than 600 nm. The electrochromic properties of the narrow band gap polymers are also of interest as the polymers show three accessible color states changing from an absorptive blue or purple in the neutral state to a transmissive sky-blue or gray in the oxidized and reduced forms. The wide electrochemical range of electrochromic activity coupled with the strong observed changes in transmissivity between oxidation states makes these materials potentially interesting for application to electrochromic displays.

We report a new fabrication approach to highly sensitive optical sensors by combining the techniques of electrospinning and electrostatic layer-by-layer adsorption. A fluorescent probe, hydrolyzed poly[2-(3-thienyl) ethanol butoxy carbonyl-methyl urethane] (H-PURET), was electrostatically assembled onto the surface of cellulose acetate (CA) electrospun nanofibrous membranes. The fluorescence of these membranes can be quenched by extremely low concentrations (ppb) of methyl viologen (MV 2+) and cytochrome c (cyt c) in aqueous solutions. This high sensitivity is attributed to the high surface-area-to-volume ratio of the electrospun membranes and efficient interaction between the fluorescent conjugated polymer and the analytes.

Relatively efficient photovoltaic devices were fabricated using blends of a phosphorescent platinum-acetylide polymer and a fullerene (PCBM); involvement of the triplet excited state of the platinum-acetylide polymer in photoinduced charge transfer is believed to contribute to the device efficiency.

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We report on two pairs of platinum acetylide based polymers and model oligomers utilizing a 2,1,3-benzothiadiazole (BTD) acceptor moiety flanked on either side by either 2,5-thienyl donor units (Pt2BTD-Th and p-PtBTD-Th) or (3,4-ethylenedioxy)-2,5-thienyl donors (Pt2BTD-EDOT and p-PtBTD-EDOT). Both oligomer/polymer pairs absorb strongly throughout the visible region; however, because the (ethylenedioxy)thiophene moiety is a stronger donor than thiophene, the latter oligomer/polymer pair has a correspondingly lower band gap and, therefore, harvests light more efficiently at longer wavelengths. p-PtBTD-Th exhibits a relatively narrow molecular weight distribution with a number-average molecular weight (Mn) of 22 kDa, while p-PtBTD-EDOT exhibits a comparable Mn of 33 kDa but has a high polydispersity index likely due to aggregation. We provide a complete report of the photophysical and electrochemical characterization of the two oligomer/polymer pairs. The photophysical studies reveal that the materials undergo relatively efficient intersystem crossing. In a discussion of the energetics of photoinduced electron transfer from the platinum polymers to [6,6]-phenyl C61 butyric acid methyl ester (PCBM), it is noted that while the singlet state is quenched efficiently, the triplet state is not quenched, indicating that charge generation in the photovoltaic materials must ensue from the singlet manifold. Finally, organic photovoltaic devices based on blends of p-PtBDT-Th or p-PtBDT-EDOT with PCBM were characterized under monochromatic and simulated solar (AM1.5) illumination. Optimized devices exhibit an open-circuit voltage (Voc) of approximately 0.5 V, a short-circuit current density (Isc) of approximately 7.2 mA cm(-2), and a fill factor of approximately 35%, which yields overall power conversion efficiencies of 1.1-1.4%.