Giulia Tregnago

Virtually pure near-infrared electroluminescence from exciplexes at polyfluorene/hexaazatrinaphthylene interfaces

Electronic processes at the heterojunction between chemically different organic semiconductors are of special significance for devices such as light-emitting diodes (LEDs) and photovoltaic diodes. Here, we report the formation of an exciplex state at the heterojunction of an electron-transporting material, a functionalized hexaazatrinaphthylene, and a hole-transporting material, poly(9,9-dioctylfluorene-alt-N-(4-butylphenyl)diphenylamine) (TFB). The energetics of the exciplex state leads to a spectral shift of ∼1 eV between the exciton and the exciplex peak energies (at 2.58 eV and 1.58 eV, respectively). LEDs incorporating such bulk heterojunctions display complete quenching of the exciton luminescence, and a nearly pure near-infrared electroluminescence arising from the exciplex (at ∼1.52 eV) with >98% of the emission at wavelengths above 700 nm at any operational voltage.

Geometric and Electronic Structures of Boron(III)-Cored Dyes Tailored by Incorporation of Heteroatoms into Ligands

Complexation of a boron atom with a series of bidentate heterocyclic ligands successfully gives rise to corresponding BF2-chelated heteroarenes, which could be considered as novel boron(III)-cored dyes. These dye molecules exhibit planar structures and expanded π-conjugated backbones due to the locked conformation with a boron center. The geometric and electronic structures of these BF2 complexes can be tailored by embedding heteroatoms in the unique modes to form positional isomer and isoelectronic structures. The structure-property relationship is further elucidated by studying the photophysical properties, electrochemical behavior and quantum-chemical calculations.

Synthesis and photophysical characteristics of polyfluorene polyrotaxanes

Summary Two alternating polyfluorene polyrotaxanes (3·TM-βCD and 3·TM-γCD) have been synthesized by the coupling of 2,7-dibromofluorene encapsulated into 2,3,6-tri-O-methyl-β- or γ-cyclodextrin (TM-βCD, TM-γCD) cavities with 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester. Their optical, electrochemical and morphological properties have been evaluated and compared to those of the non-rotaxane counterpart 3. The influence of TM-βCD or TM-γCD encapsulation on the thermal stability, solubility in common organic solvents, film forming ability was also investigated. Polyrotaxane 3·TM-βCD exhibits a hypsochromic shift, while 3·TM-γCD displays a bathochromic with respect to the non-rotaxane 3 counterpart. For the diluted CHCl3 solutions the fluorescence lifetimes of all compounds follow a mono-exponential decay with a time constant of ≈0.6 ns. At higher concentration the fluorescence decay remains mono-exponential for 3·TM-βCD and polymers 3, with a lifetime τ = 0.7 ns and 0.8 ns, whereas the 3·TM-γCD polyrotaxane shows a bi-exponential decay consisting of a main component (with a weight of 98% of the total luminescence) with a relatively short decay constant of τ1 = 0.7 ns and a minor component with a longer lifetime of τ2 = 5.4 ns (2%). The electrochemical band gap (ΔE g ) of 3·TM-βCD polyrotaxane is smaller than that of 3·TM-γCD and 3, respectively. The lower ΔE g value for 3·TM-βCD suggests that the encapsulation has a greater effect on the reduction process, which affects the LUMO energy level value. Based on AFM analysis, 3·TM-βCD and 3·TM-γCD polyrotaxane compounds exhibit a granular morphology with lower dispersity and smaller roughness exponent of the film surfaces in comparison with those of the neat copolymer 3.

Thermally induced suppression of interchain interactions in dilute aqueous solutions of conjugated polyelectrolyte rotaxanes and their analogues

We use steady-state and nanosecond time-resolved photoluminescence spectroscopy to investigate the evolution of packing interactions in dilute solutions of a sulfonated poly(diphenylenevinylene) lithium salt and its cyclodextrin-threaded polyrotaxanes as a function of the threading ratio (TR) when increasing the temperature from 10 to 40 °C. Contrary to the expectation of a temperature-induced increase of packing and aggregation, supported by previous Raman studies identifying a temperature-induced reduction in the inter-phenyl torsion angles, we find clear spectral (photoluminescence blue-shift and narrowing) and dynamic (shorter lifetimes and reduced weight of the long-lived components) signatures of a reduction of interchain interactions for the polyelectrolytes at higher temperatures with TR up to 1.3.We use steady-state and nanosecond time-resolved photoluminescence spectroscopy to investigate the evolution of packing interactions in dilute solutions of a sulfonated poly(diphenylenevinylene) lithium salt and its cyclodextrin-threaded polyrotaxanes as a function of the threading ratio (TR) when increasing the temperature from 10 to 40 °C. Contrary to the expectation of a temperature-induced increase of packing and aggregation, supported by previous Raman studies identifying a temperature-induced reduction in the inter-phenyl torsion angles, we find clear spectral (photoluminescence blue-shift and narrowing) and dynamic (shorter lifetimes and reduced weight of the long-lived components) signatures of a reduction of interchain interactions for the polyelectrolytes at higher temperatures with TR up to 1.3.

Increased luminescence efficiency by synergistic exploitation of lipo/hydrophilic co-solvency and supramolecular design

We use steady-state and time-resolved photoluminescence (PL) spectroscopy to investigate the luminescent properties of a sulfonated poly(diphenylenevinylene) lithium salt (PDV.Li) in water/propanol solutions at different concentrations, with a view to assessing its aggregation behavior. In particular, we compare results from uninsulated PDV.Li and cyclodextrin-threaded PDV.Li polyrotaxane (PDV.Li⊂β-CD). We find that addition of 1-propanol (≥20 weight%) leads to a significant blue-shift (of ∼0.20 eV) of the PL spectra, that we assign to suppressed interchain aggregation in PDV.Li solutions, with a concomitant fourfold increase in the fluorescence quantum efficiency (i.e. from 14 to 60%). Surprisingly, a moderate concentration of propanol increases further the luminescence efficiency even for PDV.Li⊂β-CD, whose supramolecular encapsulation already provides a shield against aggregation. Indeed, addition of propanol reduces the solvent polarity, and therefore helps solubilizing these materials that are still largely aromatic in nature. Interestingly, however, both uninsulated PDV.Li and polyrotaxane solutions exhibit signs of aggregation at high propanol fraction (>70%) with a distinctively weaker coupling than that of interchain states in PDV.Li at high water concentration and in pure water in particular. While we ascribe such behavior to a poor solvation of the polar moieties, we also report a different strength of aggregation for PDV.Li and PDV.Li⊂β-CD that can be attributed to the presence of the cyclodextrin rings. In PDV.Li⊂β-CD hydrogen bonding between the cyclodextrin rings may lead to closer packing between the polymer chains. We therefore suggest that a content of propanol between 30 and 70% provides a good balance of hydrophobic and hydrophilic interactions both for PDV.Li and PDV.Li⊂β-CD.

Deep-red electrophosphorescence from a platinum(II)–porphyrin complex copolymerised with polyfluorene for efficient energy transfer and triplet harvesting

A series of polyfluorene-based polymers with a range of weight percentages (w/w) of a platinum(II)-containing porphyrin, 5,15-dimesityl-10,20-diphenylporphyrinato platinum(II) (MPP(Pt)), were synthesised and incorporated into organic light-emitting diodes. All polymers showed emission predominantly in the red/NIR region with only those polymers with porphyrin w/w of less than 2% showing residual tails at wavelengths lower than 600 nm, indicating increased emission from the porphyrin as w/w increases. The 2% loading of MPP(Pt) gave the highest efficiency LED (0.48%) and light output (2630 mW/m2).

Synergic Integration of Conjugated Luminescent Polymers and Three-Dimensional Silicon Microstructures for the Effective Synthesis of Photoluminescent Light Source Arrays

In this work, a novel and straightforward technology for the fabrication of two-dimensional (2D) photoluminescent light source arrays by selective infiltration of conjugated luminescent polymers into three-dimensional (3D) silicon microstructures is presented. Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) integration into 3D silicon microstructures is investigated by means of three different deposition techniques, namely, spin-coating, dip-coating and drop-casting/slow solvent evaporation. The microstructure is fabricated by electrochemical micromachining (ECM) technology and integrates 2D arrays of square holes with different sizes (about 40 and 4 μm), spatial periods (about 70 and 10 μm), and aspect ratios (ARs) (about one and ten). Notably, square holes with higher AR can be selectively filled with polymer using spin-coating and drop-casting techniques, whereas dip-coating technique allows selective polymer filling of square holes with lower AR. Independently of size, period and AR, each polymer-infiltrated hole behaves as a single light source, thus enabling the effective synthesis of 2D photoluminescent light source arrays.