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To create low band-gap, fluorescent, and elastic organic crystal emitters, we focused on an extended π-conjugated system based on: a) a planar conformation,b) a rigid structure, and c) controlled intermolecular interactions. Herein, we report on two fluorescent and highly flexible organic crystals (1 and 2) which could bend under an applied stress. The bent crystals rapidly recover their straight shape upon release of the stress. Crystal 1 with a tetrafluoropyridyl terminal unit and a lower band-gap energy (orange emission, λ em =573 nm, Φ F =0.50), showed no bending mechanofluorochromism and had superior performance as an optical waveguide with reddish orange emission. The waveguide performance of the crystal did not decrease under bending stress. For crystal 2 with a pentafluorophenyl terminal unit (green emission, λ em =500 nm, Φ F =0.38), the original waveguide performance decreased under an applied bending stress; however, this crystal showed a unique bending mechanofluorochromism., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Five π-extended lactam-fused conjugated oligomers (5FO, 5FS, 4FPO, 4FPS, and R-4FPO) were synthesized by the tandem direct arylation. The intermolecular oxidative direct arylation was applied in the second step. These conjugated oligomers had fine-tuned FMO energies predictable by the theoretical calculation and excellent thermal stabilities. 4FPO and 4FPS bearing tetrafluoropyridine exhibited lower LUMO energy levels (-3.20 eV and -3.39 eV, respectively) compared with others. Based on the X-ray crystallography, 4FPO was found to have a herringbone crystal packing and a considerably large electron transfer integral value (137 meV). 4FPO-based bottom-gate, bottom-contact FET device demonstrated an electron mobility of 5.2×10 -3  cm 2  V -1  s -1 as a result of an edge-on alignment on the SiO 2 substrate., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Cationic Pd(II) monophosphine complexes derived from α- and β-cyclodextrins (CDs) promote the homopolymerization of styrene under carbon monoxide pressure. Although reversible CO coordination takes place under catalytic conditions according to (13) C NMR studies with (13) C-enriched CO, both complexes catalyze the formation of CO-free styrene polymers. These macromolecules display optical activity as a result of the presence of stereoregular sequences within the overall atactic polymer., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dipalladium complexes of a cyclic bis(diimine) ligand with a double-decker structure catalyze polymerization of ethylene and α-olefins and copolymerization of ethylene with 1-hexene. The polymerization of 1-hexene yields a polymer that is mainly composed of the hexamethylene unit formed by 2,1-insertion of the monomer into the palladium-carbon bond, followed by chain-walking (6,1-insertion). The polymerization of 4-methyl-1-pentene proceeds by 2,1-insertion with a selectivity of 92-97 %, and affords the polymer with methyl and 2-methylhexyl branches. 2,1-Insertion occurs selectively in all of the polymerization reactions of α-olefins catalyzed by the dipalladium complexes. Ethylene polymerization with the catalyst at 100 °C lasts over 24 h, whereas the monopalladium-diimine catalyst loses its activity within 8 h at 60 °C. Polyethylene obtained by the dipalladium catalyst is less-branched and has a higher molecular weight compared to that of the monopalladium catalyst under the same conditions. Copolymerization of ethylene with 1-hexene affords solid products with melting points and molecular weights that vary depending on the polymerization time, suggesting formation of a block and/or gradient copolymer., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A dipalladium complex with a double-decker structure catalyzes ethylene-acrylate copolymerization to produce the branched polymer containing the acrylate units in the polymer chain, not at the branch terminus. The cooperation of the two palladium centers, which are fixed in a rigid framework of the macrocyclic ligand, is proposed to have a significant dinuclear effect on the copolymerization., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Cationic Pd complexes, prepared from [PdCl(ArN=C(12)H(6)=NAr)(Me)] and Na[B{3,5(CF(3))(2)C(6)H(3)}(4)] (NaBARF), catalyze the cyclopolymerization of 4,4-disubstituted 1,6-heptadienes. The polymers produced contain a trans-fused five-membered ring in each repeating unit. NMR spectroscopy and FAB mass spectrometry of the polymers formed indicated that the initiation end of the chain contains either the cyclopentyl group derived from the preformed Pd-monomer complex or a hydrogen atom left on the Pd center by the chain-transfer reaction. The stable cyclopentylpalladium species are involved in both initiation and propagation steps and undergo isomerization into (cyclopentylmethyl)palladium species followed by the insertion of a CH=CH(2) bond of a new monomer molecule into the Pd-CH(2) bond. Copolymerization of 1,6-heptadiene derivatives with ethylene, catalyzed by the Pd complexes, yields polymers that contain trans five-membered rings and branched oligoethylene units. Copolymerization of isopropylidene diallylmalonate with 1-hexene affords a polymer with 26% diene incorporation. The copolymerization consumes 1-hexene more readily than isopropylidene diallylmalonate, although gel permeation chromatography and NMR spectroscopy of the polymers produced show the formation of copolymers rather than of a mixture of homopolymers. Polymerization of 1-hexene initiated with a Pd-barbiturate complex and terminated with 5-allyl-5-hexylpyrimidine-2,4,6(1H,3H,5H)-trione/Et(3)SiH leads to polyhexene with barbiturate moieties at both terminal ends. Addition of 5-hexyl-2,4,6-triaminopyrimidine to a toluene solution of the telechelic poly(1-hexene) converts the solution into gel.

Selective 2,1-insertion of the monomer and subsequent elimination of the β-carbon atom of the growing polymer end is proposed as a new mechanism for polymer synthesis that involves ring opening of the monomer. A palladium complex promotes the ring-opening polymerization of 1-methylene-2-arylcyclopropanes to afford polymers with a vinylidene group in each monomer unit., (© 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.)