Enhanced solubility of novel poly(benzoxazole)s with a soft linkage and a rigid pendant group

Aromatic poly(benzoxazole)s are a class of rigid‐rod conjugated polymers. However, their poor solubility in organic solvents limits potential applications. Thus, a good method that can address this dilemma is needed, given that existing methods involve models with either poor solubility but good thermal stability or good solubility but poor thermal stability. In this paper we report a novel aromatic poly(benzoxazole) with a soft linkage and a rigid pendant group. Structural characterizations of the polymers via Fourier transform infrared and proton nuclear magnetic resonance spectroscopy reveal the formation of a benzoxazole ring and an imide ring. The introduction of rigid pendant groups improved the solubility and enhanced the thermal stability of the polymer, which was impaired by the incorporation of the soft linkage. Most of these polymers are soluble at room temperature or when heated in dimethyl sulfoxide, N,N‐dimethylformamide or N,N‐dimethylacetamide. Some polymers can even be dissolved in m‐cresol and tetrahydrofuran. A 10% weight loss in these polymers was observed at temperatures over 410 °C. Moreover, the incorporation of the imide pendant group increased the conjugation length of the polymer structural unit and accelerated electron delocalization. Copyright © 2012 Society of Chemical Industry     

Photoactivation and Detection of Photoexcited Molecules and Photochemical Products

Aerobic photoactivation of photosensitizing dye molecules can lead to the formation of oxygen radicals, singlet oxygen and other partially reduced oxygen species, collectively called reactive oxygen species (ROS), which are responsible for photodynamic damage and the accompanying cytotoxicity. This review briefly describes basic photophysical phenomena involved in the formation of electronically excited states and photochemical processes that play a key role in the generation of ROS. Physicochemical properties of the excited states of the photosensitizing dye molecules and of ROS, particularly their chemical reactivity with selected substrate molecules, as well as major spectroscopic and analytical methods used for the detection and characterization of reactive intermediates involved in photodynamic phenomena, are critically discussed in this paper.     

Quantum Control Landscape for a Λ-atom in the Vicinity of Second-Order Traps

We show that the second-order traps in the control landscape for a three-level Λ-system found in our previous work (Phys. Rev. Lett. 2011 , 106, 120402) are not local maxima: there exist directions in the space of controls in which the objective grows. The growth of the objective is slow — at best 4th order for weak variations of the control. This implies that simple gradient methods would be problematic in the vicinity of second-order traps, where more sophisticated algorithms that exploit the higher order derivative information are necessary to climb up the control landscape efficiently. The theory is supported by a numerical investigation of the landscape in the vicinity of the ε(t)=0 second-order trap, performed using the GRAPE and BFGS algorithms.     

Novel 1,4‐diketo‐3,6‐diphenyl pyrrolo[3,4‐c]pyrrole (DPP)‐based copolymers with large Stokes shift

Two novel alternating π‐conjugated copolymers, named PDPPDOPV and PDPPDOPE, constituted of 1,4‐diketo‐3,6‐diphenyl pyrrolo[3,4‐c]pyrrole (DPP) with 2,5‐dioctyloxy‐1,4‐phenylenevinylene (DOPV) or 2,5‐dioctyloxy‐1,4‐phenyleneethynylene (DOPE), respectively, were synthesized and characterized by UV‐vis, FT‐IR, and photoluminescence spectroscopy. They are dark red solid readily soluble in various common organic solvents including THF and chloroform. The UV‐vis absorption spectra of the polymers show strong absorption bands, which correspond to the π‐π* transition of π‐conjugated segments. Photoluminescence (PL) spectra show that both polymer films and solution have large Stokes shifts. From their fluorescence behavior, Stokes shifts of 173 nm and 199 nm are derived for the films of PDPPDOPV and PDPPDOPE, respectively, which are the largest two values ever reported for DPP‐containing polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Tuning the size and optical properties in molecular nano/microcrystals: manifestation of hierarchical interactions

Intermolecular interactions, such as hydrogen bonding, dipolar and van der Waals, occurring in molecular crystals cover a range of magnitudes. As the crystal evolves from a relatively softer state in the nanoscopic size regime to a harder one in the microcrystalline and bulk solid state, the impact of the hierarchy of intermolecular interactions can be expected to emerge in a progressive fashion. The strongest interactions alone would be manifested at small sizes; as the crystal grows, the effect of the weaker ones will be added on, with the bulk crystals exhibiting the cumulative impact of the different interactions. We demonstrate this phenomenon through investigations of the solution, colloid, and solid state of a novel zwitterionic molecule based on the diaminodicyanoquinodimethane framework. A reprecipitation-digestion protocol is developed for the fabrication of nano/microcrystals of varying sizes. Microscopic and spectroscopic characterizations reveal tuning of the size and optical properties of this material. The optical absorption of the colloidal particles evolves with size towards that of the bulk solid, the emission showing a steady enhancement of intensity. Crystallographic investigations coupled with semiempirical computations provide a viable model to describe the range of observations in terms of the gradual accumulation of hierarchical intermolecular interactions.     

Unique UV absorbance for triphenylimidazole‐based polymer

In this study, a novel vinyl polymer containing 2,4,5‐triphenylimidazole side groups was synthesized through conventional radical polymerization, which possesses the characteristic of temperature‐dependent absorbance in the near‐ultraviolet (UV) spectral region. The linear dependence of UV absorbance on temperature was confirmed for the polymer both in solid state and in solution by experiment and also supported by the results of theoretical investigation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dependence of optical properties on the preparation methods of poly[(9,9′‐dialkylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)]

A blue‐light‐emissive fluorene‐based polyoxadiazole, an n‐type polyfluorene derivative, was synthesized by both one‐step and two‐step methods. Directly polymerized poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx‐DP) exhibited a higher molecular weight and a more efficient photoluminescence quantum yield than poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx) prepared via a polyhydrazide precursor, poly[9,9′‐didodecylfluorene‐2,7‐(2,5‐dihydrazide‐ 1,3,4‐oxadiazole). Both polymers, differently prepared, showed similar photoluminescent properties in 1,2‐dichloroethane. However, in a film state, the influence of the interchain interactions on the photoluminescence of PFOx with the lower molecular weight was larger than on the photoluminescence of PFOx‐DP. The electron‐deficient property of an oxadiazole group in the polymer backbone resulted in low‐lying highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of ?6.29 and ?3.26eV, respectively, of the polymer suitable for electron‐transport/hole‐blocking layers and emissive layers in multilayer electroluminescence devices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3112–3118, 2004     

Morphology and Photophysical Properties of Electrospun Light‐Emitting Polystyrene/Poly(p‐phenylene ethynylene) Fibers

Ultra‐thin fibers, consisting of blends of a PPE derivative and polystyrene, with average diameters ranging from 430 to 1 200 nm, were produced by electrospinning. The electrospinnability was significantly improved by adding pyridinium formate to the spinning solution. FT‐IR spectroscopy was used to confirm the composition of the electrospun fibers and their morphology was probed by SEM. The optical properties of the as‐prepared solutions, pristine and annealed fibers, and corresponding spin‐coated and solution‐cast films were investigated by UV‐vis spectroscopy. A comparison of the PL emission spectra revealed aggregation of PPE molecules in the electrospun materials but the extent of aggregation can be reduced if the materials are annealed above the glass transition temperature.

     

Triplet Harvesting from Intramolecular Singlet Fission in Polytetracene

Singlet fission (SF), a promising mechanism of multiple exciton generation, has only recently been engineered as a fast, efficient, intramolecular process (iSF). The challenge now lies in designing and optimizing iSF materials that can be practically applied in high‐performance optoelectronic devices. However, most of the reported iSF systems, such as those based on donor–acceptor polymers or pentacene, have low triplet energies, which limits their applications. Tetracene‐based materials can overcome significant challenges, as the tetracene triplet state is practically useful, ≈1.2 eV. Here, the synthesis and excited state dynamics of a conjugated tetracene homopolymer are studied. This polymer undergoes ultrafast iSF in solution, generating high‐energy triplets on a sub‐picosecond time scale. Magnetic‐field‐dependent photocurrent measurements of polytetracene‐based devices demonstrate the first example of iSF‐generated triplet extraction in devices, exhibiting the potential of iSF materials for use in next‐generation devices.