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Exciton behavior is crucial for improving the optoelectronic property of a light‐emitting conjugated polymer. Herein, the photoexcitation dynamics of exciton migration and energy transfer in a self‐doped β‐conformation film of the polydiarylfluorenes (poly[4‐(octyloxy)‐9,9‐diphenylfluoren‐2,7‐diyl]‐co‐[5‐(octyloxy)‐9,9‐ diphenylfluoren‐2,7‐diyl], PODPF) are demonstrated. Compared to the first generation of the β‐conformation polyfluorene, poly(9,9‐dioctylfluorene) (PFO), energy transfer occurs in PODPF β‐conformation films in a time period of ≈150 ps, much longer than those of the PFO ones (<5 ps), associated with the effective intrachain energy transfer (few hundred picoseconds), rather than interchain Förster energy transfer (a few picoseconds). Similar to PFO, the PODPF β‐conformation also displays well‐resolved vibronic emission peaks at 20 K, attributed to the planar and rigid conformation. Interestingly, a residual 0‐0 band emission of nonplanar conformation chain segments (435 nm, 2.85 eV) at 20 K also further confirms the exciton migration from the amorphous state to the β‐conformation domain in PODPF films. Therefore, the stable dual amplified spontaneous emission (ASE) behavior of the PODPF self‐doped films at 461 nm (2.69 eV) and 483 nm (2.57 eV), originates from the individual amorphous and β‐conformation domains. [ABSTRACT FROM AUTHOR]

ABSTRACT Poly(phenylene methylene) (PPM) exhibits pronounced blue fluorescence in solutions as well as in the solid state despite its non-π-conjugated nature. Optical spectroscopy was used to explore the characteristics and the physical origin of its unexpected optical properties, namely absorption in the 350-450 nm and photoluminescence in the 400-600 nm spectral regions. It is shown that PPM possesses two discrete optically active species, and a relatively long photoluminescence lifetime (>8 ns) in the solid-state. Given the evidence reported herein, π-stacking and aggregation/crystallization, as well as the formation of anthracene-related impurities, are excluded as the probable origins of the optical properties. Instead there is sufficient evidence that PPM supports homoconjugation, that is: π-orbital overlap across adjacent repeat units enabled by particular chain conformation(s), which is confirmed by DFT calculations. Furthermore, poly(2-methylphenylene methylene) and poly(2,4,6-trimethylphenylene methylene) - two derivatives of PPM - were synthesized and found to exhibit comparable spectroscopic properties, confirming the generality of the findings reported for PPM. Cyclic voltammetry measurements revealed the HOMO-LUMO gap to be 3.2-3.3 eV for all three polymers. This study illustrates a new approach to the design of light-emitting polymers possessing hitherto unknown optical properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 707-720 [ABSTRACT FROM AUTHOR]

ABSTRACT Solution-crystallization is studied for two polyfluorene polymers possessing different side-chain structures. Thermal analysis and temperature-dependent optical spectroscopy are used to clarify the nature of the crystallization process, while X-ray diffraction and scanning electron microscopy reveal important differences in the resulting microstructures. It is shown that the planar-zigzag chain conformation termed the β-phase, which is observed for certain linear-side-chain polyfluorenes, is necessary for the formation of so-called polymer-solvent compounds for these polymers. Introduction of alternating fluorene repeat units with branched side-chains prevents formation of the β-phase conformation and results in non-solvated, i.e. melt-crystallization-type, polymer crystals. Unlike non-solvated polymer crystals, for which the chain conformation is stabilized by its incorporation into a crystalline lattice, the β-phase conformation is stabilized by complexation with solvent molecules and, therefore, its formation does not require specific inter-chain interactions. The presented results clarify the fundamental differences between the β-phase and other conformational/crystalline forms of polyfluorenes. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1492-1506 [ABSTRACT FROM AUTHOR]

ABSTRACT Polymer-solvent compound formation, occurring via co-crystallization of polymer chains and selected small-molecular species, is demonstrated for the conjugated polymer poly(9,9-dioctylfluorene) (PFO) and a range of organic solvents. The resulting crystallization and gelation processes in PFO solutions are studied by differential scanning calorimetry, with X-ray diffraction providing additional information on the resulting microstructure. It is shown that PFO-solvent compounds comprise an ultra-regular molecular-level arrangement of the semiconducting polymer host and small-molecular solvent guest. Crystals form following adoption of the planar-zigzag β-phase chain conformation, which, due to its geometry, creates periodic cavities that accommodate the ordered inclusion of solvent molecules of matching volume. The findings are formalized in terms of nonequilibrium temperature-composition phase diagrams. The potential applications of these compounds and the new functionalities that they might enable are also discussed. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1481-1491 [ABSTRACT FROM AUTHOR]

ABSTRACT We present a study of isotropic and uniaxially oriented binary blend films comprising ≤1 wt % of the conjugated polymer poly(9,9-dioctylfluorene) (PFO) dispersed in both ultra-high molecular weight (UHMW) and linear-low-density (LLD) polyethylene (PE). Polarized absorption, fluorescence and Raman spectroscopy, scanning electron microscopy, and X-ray diffraction are used to characterize the samples before and after tensile deformation. Results show that blend films can be prepared with PFO chains adopting a combination of several distinct molecular conformations, namely glassy, crystalline, and the so-called β-phase, which directly influences the resulting optical properties. Both PFO concentration and drawing temperature strongly affect the alignment of PFO chains during the tensile drawing of the blend films. In both PE hosts, crystallization of PFO takes place during drawing; the resulting ordered chains show optimal optical anisotropy. Our results clarify the PFO microstructure in oriented blends with PE and the processing conditions required for achieving the maximal optical anisotropy. © 2014 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 22-38 [ABSTRACT FROM AUTHOR]

The ability to modify or enhance the dielectric constant of semiconducting polymers can prove valuable for a range of optoelectronic and microelectronic applications. In the case of organic photovoltaics, increasing the dielectric constant of the active layer has often been suggested as a method to control charge generation, recombination dynamics, and ultimately, the power conversion efficiencies. In this contribution, the impact that the degree and pattern of fluorination has on the dielectric constant of poly(3‐octylthiophene) (P3OT), a more soluble analogue of the widely studied conjugated material poly(3‐hexylthiophene), is explored. P3OT and its backbone‐fluorinated analogue, F‐P3OT, are compared along with a block and alternating copolymer version of these materials. It is found that the dielectric constant of the polymer thin films increases as the degree of backbone fluorination increases, in a trend consistent with density functional theory calculations of the dipole moment. The impact of the degree and pattern of backbone fluorination on the dielectric constant of a series of soluble conjugated poly(3‐octylthiophenes) is investigated. It is found that the low‐frequency dielectric constant of the polymer thin films increases as the degree of backbone fluorination increases, in a trend consistent with density functional theory calculations of the dipole moment. [ABSTRACT FROM AUTHOR]