Masahiro Rikukawa

Synthesis of optically active regioregular polythiophenes and their self-organization at the air-water interface.

Regioregular polythiophenes containing an optically active substituent in the third position of the thiophene ring, head-to-tail poly(3-[2-((S)-1-methyloctyloxy)ethyl]thiophene)s (HT-P(S)MOETs), were synthesized using highly reactive zinc. For comparison, HT-P(R)MOET and achiral HT-P(±)MOET also were synthesized from R-type monomers and racemic monomers, respectively. The HT-PMOET possessed greater than 95% head-to-tail coupling with a weight-average molecular weight (Mw) between 1.96 × 10(4) and 2.94 × 10(4). The polymers were characterized using (1)H and (13)C NMR, optical rotatory power measurements, circular dichroism (CD), and UV-vis spectroscopy. X-ray diffraction patterns of the cast films demonstrated that regioregular HT-PMOET possessed a strong tendency to self-assemble into highly ordered, crystalline structures. The HT-P(S)MOET and HT-P(R)MOET showed strong Cotton effects, while HT-P(±)MOET showed very weak Cotton effects. The presence of a circular dichroism effect indicated that the side chain chirality induced optical activity in poly(thiophene) main chains. The monolayer formation of HT-PMOET spread on the water surface was characterized using a pressure-area (π-A) isotherm. The molecular areas of HT-P(S)MOET and HT-P(R)MOET molecules on the water surface were 33.5 and 32.9 Å(2), respectively, at 10 °C, which were larger than that of HT-P(±)MOET (27.9 Å(2)), suggesting that optically active HT-PMOET expanded because of the chiral repulsion between side chains. Multilayer films of HT-PMOET were prepared by repeating horizontal deposition of the monolayer on the water surface. The multilayer films of optically active HT-PMOET obtained showed stronger Cotton effects than did the cast films. In addition, electrical conductivities of HT-PMOET multilayer films were superior to those of spin-coated films. Head-to-tail poly(3-[2-((S)-1-methylpropyloxy)ethyl]thiophene) (HT-P(S)MPET), which contained shorter side chain lengths compared to HT-P(S)MOET, also was synthesized. The CD intensities of HT-P(S)MPET multilayer films were smaller than those of HT-P(S)MOET multilayer films, suggesting that the optically active side-chain length is critically important to the optically active self-assembly.

Synthesis and Characterization of Polythiophenes Having Phosphonate Ester Groups

Polythiophene derivatives containing a phosphonate ester group, poly [3-(3-diethyl-phosphonate) propoxythiophene] (PEPPT), were synthesized by Rieke and oxidative polymerization methods. These PEPPTs were soluble in polar organic solvents such as methanol, DMF, and chloroform. The head-to-tail ratio of PEPPT (Rieke) was estimated to be 98 % by 1H NMR spectroscopy, while that of PEPPT (Oxidative) was estimated to be 53 %. The maximum absorption peak of PEPPT (Rieke) was observed at 596 nm, which was 46 nm longer than that of PEPPT (Oxidative) in CHCl3 solutions. This result suggests that the planarity of PEPPT (Rieke) is higher than that of PEPPT (Oxidative) due to the high regioregularity of the side chains. The estimated band gap of PEPPT was 1.60 eV for Rieke-synthesized derivatives. The XRD peak of PEPPT(Rieke) was observed at 5.14º (17.2 Å) and that of PEPPT (Oxidative) was not clearly observed, suggesting that PEPPT(Rieke) has self-organized properties to form a layered structure.

Fabrication of Organic-Inorganic Nano-Hybrid Materials Containing Oligothiophene Derivatives

Oligothiophene derivatives, 4,4’-bis-(2-aminoethylthienyl)-3,4-ethylenedioxythiophene dihydrohalide (AET-EDOT·HX: X = I, Br), were synthesized by Grignard coupling reactions. The hybrid films of oligothiophene and lead halide were fabricated by casting and spin-coating methods. The effect of halogen species on the optical properties of the perovskites was investigated. The X-ray diffraction profiles of (AET-EDOT)PbX4 cast films indicated that the layered structures were formed by the self-organization. After hybridization of AET-EDOT·HX with PbX2, new absorption peaks due to the confined excitons were observed at 400 nm for (AET-EDOT)PbBr4 film, and at 395 nm for (AET-EDOT)PbI4 film. These results indicated that the diamino-type oligothiophenes were successfully incorporated into the organic-inorganic layered perovskites. AFM images of (AET-EDOT)PbX4 cast films showed polycrystalline grains, indicating that the polycrystalline structures covered on the substrate surface.

Synthesis and Characterization of Organic-Inorganic Layered Perovskite Compounds Using Fullerene Derivatives

Layered perovskite (RNH3)2PbI4 (R = organic cation), which contained the fullerene derivatives, [ethyl-3-tert-butoxycarbonylaminopropyl (1,2-methanofullerene C60)]-61,61-di carboxylate iodide (EAF-I) and di [3-tert-butoxycarbonylaminopropyl (1,2-methanofullerene C60)]- 61,61-dicarboxylate diiodide (DAF-I2) in the organic layers were fabricated and compared with previously reported perovkite compound containing N-methyl-2-(4-aminophenyl)-fulleropyrrolidine iodide (AmPF-I). Because the solvent solubilities of EAF-I and DAF-I2 to N,N-dimethylformamide (DMF) were higher than AmPF-I, the film processability of EAF-I and DAF-I2 was improved compared with AmPF-I. The X-ray diffraction patterns proved the construction of the perovskite structure in (EAF)2PbI4 and (AmPF)2PbI4 cast films. EAF was well-organized and closer-packing than AmPF in the perovskite structure. For the diamine-type fullerene, DAF-I2, it is difficult to form layered structure by spin-coated or cast methods. New sharp X-ray diffraction peaks were observed for DAF-I2 films dipped in PbI2 solution. The intercalations and formation of perovskite structure of (DAF)PbI4 were studied.

Synthesis and Fabrication of Aligned Conjugated Polymer Thin Films

Fluorene-thiophene copolymers having chiral and azobenzene substituents, PAzB4-T, were synthesized by the Pd-catalyzed Suzuki coupling method. We studied the aligning organization of the main chain of PAzB4-T with the activation of the attached functional groups by thermal annealing and photo-annealing processes. Circular dichroism (CD) measurements revealed that the thermally annealed PAzB4-T spin-coated films exhibited bisignate Cotton effects over the absorption regions of the polymer main chains and the azobenzene side chains due to the formation of chiral assemblies. After the photo-annealing process, which means linearly polarized light irradiation accompanied by thermal annealing, the PAzB4-T spin-coated films showed linear dichroism over the absorption region of the main chains, due to the alignment of azobenzene side chains against the electric field of the linearly polarized light. These results suggested that rigid conjugated polymers were successfully aligned by the alignment of functional groups with the external stimuli.