Study on effect of supercritical CO2 on structural ordering and charge transporting property in thiophene-based block copolymer

We reported that supercritical (sc) annealing of poly(3-hexylthiophene) (P3HT), and its block copolymers with poly(ethylene oxide) (PEO) and polystyrene (PSt) brought about improvements in the crystal structure and hole mobility, determined by the space charge limited current (SCLC) measurement. P3HT-b-PEO showed the largest increase in mobility. From XRD profile, it was found that the treatment with scCO2 increased the crystallite size and crystallinity. UV-vis spectra showed that the effective conjugation length in the scCO2 treated films was increased compared to the as-spun, suggesting that CO2 molecules are incorporated into domains of the second block domains and P3HT amorphous region, and assist to alter the characteristics of the crystalline region. Then, it was considered that the change in the crystalline structure and the improvement of P3HT chains packing led to the enhanced mobility. Since PEO is known to have a higher affinity for CO2, the increase of mobility was specifically intensive.

Designing Red-Shifted Molecular Emitters Based on the Annulated Locked GFP Chromophore Derivatives

Bioimaging techniques require development of a wide variety of fluorescent probes that absorb and emit red light. One way to shift absorption and emission of a chromophore to longer wavelengths is to modify its chemical structure by adding polycyclic aromatic hydrocarbon (PAH) fragments, thus increasing the conjugation length of a molecule while maintaining its rigidity. Here, we consider four novel classes of conformationally locked Green Fluorescent Protein (GFP) chromophore derivatives obtained by extending their aromatic systems in different directions. Using high-level ab initio quantum chemistry calculations, we show that the alteration of their electronic structure upon annulation may unexpectedly result in a drastic change of their fluorescent properties. A flip of optically bright and dark electronic states is most prominent in the symmetric fluorene-based derivative. The presence of a completely dark lowest-lying excited state is supported by the experimentally measured extremely low fluorescence quantum yield of the newly synthesized compound. Importantly, one of the asymmetric modes of annulation provides a very promising strategy for developing red-shifted molecular emitters with an absorption wavelength of ∼600 nm, having no significant impact on the character of the bright S-S1 transition.

Doubly linked chiral phenanthrene oligomers for homogeneously π-extended helicenes with large effective conjugation length

Helically twisted conductive nanocarbon materials are applicable to optoelectronic and electromagnetic molecular devices working on the nanometer scale. Herein, we report the synthesis of per-peri-perbenzo[5]- and [9]helicenes in addition to previously reported π-extended [7]helicene. The homogeneously π-extended helicenes can be regarded as helically fused oligo-phenanthrenes. The HOMO−LUMO gap decreased significantly from 2.14 to 1.15 eV with increasing helical length, suggesting the large effective conjugation length (ECL) of the π-extended helical framework. The large ECL of π-extended helicenes is attributed to the large orbital interactions between the phenanthrene subunits at the 9- and 10-positions, which form a polyene-like electronic structure. Based on the experimental results and DFT calculations, the ultrafast decay dynamics on the sub-picosecond timescale were attributed to the low-lying conical intersection.