NIR Phosphorescent Intramolecularly Bridged Benzoporphyrins and Their Application in Oxygen-Compensated Glucose Optode.

A glucose optode measuring the internal oxygen gradient is presented. The multilayer biosensor is composed of (i) analyte-impermeable transparent support, (ii) first oxygen-sensing layer combined with an enzymatic layer, (iii) diffusion barrier, and (iv) second oxygen-sensing layer. To make this design suitable for measurement in subcutaneous tissue, a pair of NIR phosphorescent indicators with very different spectral properties is chosen. Combination of a conventional Pt(II) tetrabenzoporphyrin dye (absorption and emission maxima at 617 and 772 nm, respectively) used in the first layer and a new intramolecularly bridged Pt(II) complex (absorption and emission maxima at 673 and 872 nm, respectively) in the second layer enables efficient separation of both emission signals. This specially designed dye class is accessible via Scholl-reaction from tetraphenyltetrabenzoporphyrin complexes. For the first time, the new optode allows simultaneous glucose and oxygen measurement in a single spot and therefore accurate compensation of oxygen heterogeneities resulting from fluctuations in the tissue. The presented material covers the dynamic ranges from 0 to 150 hPa O2 and from 0 to 360 mg/dL (20 mM) glucose (at 37 °C).

Short-Term Environmental Effects and Their Influence on Spatial Homogeneity of Organic Solar Cell Functionality.

In this study, we focus on the induced degradation and spatial inhomogeneity of organic photovoltaic devices under different environmental conditions, uncoupled from the influence of any auxiliary hole-transport (HT) layer. During testing of the corresponding devices comprising the standard photoactive layer of poly(3-hexylthiophene) as donor, blended with phenyl-C61-butyric acid methyl ester as acceptor, a comparison was made between the nonencapsulated devices upon exposure to argon in the dark, dry air in the dark, dry air with illumination, and humid air in the dark. The impact on the active layer's photophysics is discussed, along with the device physics in terms of integral solar cell performance and spatially resolved photocurrent distribution with point-to-point analysis of the diode characteristics to determine the origin of the observed integrated organic photovoltaic device behavior. The results show that even without the widely used hygroscopic HT layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), humidity is still a major factor in the short-term environmental degradation of organic solar cells with this architecture, and not only oxygen or light, as is often reported. Different from previous reports where water-induced device degradation was spatially homogeneous and formation of Al2O3 islands was only seen for oxygen permeation through pinholes in aluminum, we observed insulating islands merely after humidity exposure in the present study. Further, we demonstrated with laser beam induced current mapping and point-to-point diode analysis that the water-induced performance losses are a result of the exposed device area comprising regions with entirely unaltered high output and intact diode behavior and those with severe degradation showing detrimentally lowered output and voltage-independent charge blocking, which is essentially insulating behavior. It is suggested that this is caused by transport of water through pinholes to the organic/metal interface, where they form insulating oxide or hydroxide islands, while the organic active layer stays unharmed.

Electron-Deficient Near-Infrared Pt(II) and Pd(II) Benzoporphyrins with Dual Phosphorescence and Unusually Efficient Thermally Activated Delayed Fluorescence: First Demonstration of Simultaneous Oxygen and Temperature Sensing with a Single Emitter.

We report a family of Pt and Pd benzoporphyrin dyes with versatile photophysical properties and easy access from cheap and abundant chemicals. Attaching 4 or 8 alkylsulfone groups onto a meso-tetraphenyltetrabenzoporphyrin (TPTBP) macrocylcle renders the dyes highly soluble in organic solvents, photostable, and electron-deficient with the redox potential raised up to 0.65 V versus the parent porphyrin. The new dyes intensively absorb in the blue (Soret band, 440-480 nm) and in the red (Q-band, 620-650 nm) parts of the electromagnetic spectrum and show bright phosphorescence at room-temperature in the NIR with quantum yields up to 30% in solution. The small singlet-triplet energy gap yields unusually efficient thermally activated delayed fluorescence (TADF) at elevated temperatures in solution and in polymeric matrices with quantum yields as high as 27% at 120 °C, which is remarkable for benzoporphyrins. Apart from oxygen sensing, these properties enable unprecedented simultaneous, self-referenced oxygen and temperature sensing with a single indicator dye: whereas oxygen can be determined either via the decay time of phosphorescence or TADF, the temperature is accessed via the ratio of the two emissions. Moreover, the dyes are efficient sensitizers for triplet-triplet annihilation (TTA)-based upconversion making possible longer sensitization wavelength than the conventional benzoporphyrin complexes. The Pt-octa-sulfone dye also features interesting semireversible transformation in basic media, which generates new NIR absorbing species.

Synthesis of a conjugated pyrrolopyridazinedione-benzodithiophene (PPD-BDT) copolymer and its application in organic and hybrid solar cells.

ABSTRACT: Herein, we describe the synthesis and characterization of a conjugated donor-acceptor copolymer consisting of a pyrrolopyridazinedione (PPD) acceptor unit, and a benzodithiophene (BDT) donor unit. The polymerization was done via a Stille cross-coupling polycondensation. The resulting PPD-BDT copolymer revealed an optical bandgap of 1.8 eV and good processability from chlorobenzene solutions. In an organic solar cell in combination with PC70BM, the polymer led to a power conversion efficiency of 4.5%. Moreover, the performance of the copolymer was evaluated in polymer/nanocrystal hybrid solar cells using non-toxic CuInS2 nanocrystals as inorganic phase, which were prepared from precursors directly in the polymer matrix without using additional capping ligands. The PPD-BDT/CuInS2 hybrid solar cells showed comparably high photovoltages and a power conversion efficiency of 2.2%.