start-ver=1.4 cd-journal=joma no-vol=58 cd-vols= no-issue=3 article-no= start-page=1571 end-page=1577 dt-received= dt-revised= dt-accepted= dt-pub-year=2025 dt-pub=20250203 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Synthesis and Postfunctionalization of Acrylate-Appended Poly(cyclohexene carbonate)s: Modulation of Properties of CO2-Based Polymers en-subtitle= kn-subtitle= en-abstract= kn-abstract=Functional CO2-based polycarbonates are expected to be sustainable materials. Herein, a bifunctional aluminum porphyrin catalyzed the terpolymerization of cyclohexene oxide (CHO), acrylate-appended CHO, and CO2 to provide poly(cyclohexene carbonate)s (PCHCs) with acrylate groups. Postfunctionalization of PCHCs via Michael addition or Heck reaction enabled the incorporation of thiol, amine, and aromatics into PCHCs with high selectivity and efficiency. PCHCs with the flexible long alkyl chains showed a glass-transition temperature (Tg) of down to 52 ‹C, which was much lower than that of PCHC (127 ‹C). In sharp contrast, PCHCs with rigid pyrenyl groups showed Tg values of up to 152 ‹C and fluorescence emission. Thus, a wide range of polymers were obtained by robust and sustainable synthetic methods, and the functional groups modulated the properties of the CO2-based polycarbonates. en-copyright= kn-copyright= en-aut-name=MaedaChihiro en-aut-sei=Maeda en-aut-mei=Chihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=InoueHina en-aut-sei=Inoue en-aut-mei=Hina kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=EmaTadashi en-aut-sei=Ema en-aut-mei=Tadashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=61 cd-vols= no-issue=25 article-no= start-page=4757 end-page=4773 dt-received= dt-revised= dt-accepted= dt-pub-year=2025 dt-pub=2025 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Recent development of azahelicenes showing circularly polarized luminescence en-subtitle= kn-subtitle= en-abstract= kn-abstract=Recently, a variety of circularly polarized luminescence (CPL) dyes have been developed as next-generation chiroptical materials. Helicenes, ortho-fused aromatics, have been recognized as some of the most promising CPL dyes. Although typical carbohelicenes show CPL, weak fluorescence is often emitted in the blue region. In contrast, heteroatom-embedded helicenes (heterohelicenes) can show intense fluorescence and CPL in the visible region because heteroatoms alter the electronic states of helicene frameworks. Among various heterohelicenes, nitrogen-embedded helicenes (azahelicenes) have unique features such as facile functionalization and sensitive responses to acid/base or metal ions. Furthermore, polycyclic aromatic hydrocarbons (PAHs) containing azaborine units have been recognized as excellent luminescent materials, and the helical derivatives, B,N-embedded helicenes, have been rapidly growing recently. In this feature article, we review and summarize the synthesis and chiroptical properties of azahelicenes, which are classified into imine-type and amine-type azahelicenes and B,N-embedded helicenes. CPL switching systems of azahelicenes are also reviewed. en-copyright= kn-copyright= en-aut-name=MaedaChihiro en-aut-sei=Maeda en-aut-mei=Chihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=EmaTadashi en-aut-sei=Ema en-aut-mei=Tadashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=64 cd-vols= no-issue=8 article-no= start-page=e202418546 end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2025 dt-pub=20250122 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=B,N]Embedded Helical Nanographenes Showing an Ion]Triggered Chiroptical Switching Function en-subtitle= kn-subtitle= en-abstract= kn-abstract=Intramolecular oxidative aromatic coupling of 3,6-bis(m-terphenyl-2f-yl)carbazole provided a bis(m-terphenyl)-fused carbazole, while that of 3,6-bis(m-terphenyl-2f-yl)-1,8-diphenylcarbazole afforded a bis(quaterphenyl)-fused carbazole. Borylation of the latter furnished a B,N-embedded helical nanographene binding a fluoride anion via a structural change from the three-coordinate boron to the four-coordinate boron. The anionic charge derived from the fluoride anion is stabilized over the expanded ƒΞ-framework, which leads to the high binding constant (Ka) of 1~105?M?1. The four-coordinate boron species was converted back to the parent three-coordinate boron species with Ag+, and the chiroptical switch between the three-coordinate boron and four-coordinate boron species has been achieved via the ion recognition with the change in the color and glum values. en-copyright= kn-copyright= en-aut-name=MaedaChihiro en-aut-sei=Maeda en-aut-mei=Chihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=MichishitaSayaka en-aut-sei=Michishita en-aut-mei=Sayaka kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=YasutomoIssa en-aut-sei=Yasutomo en-aut-mei=Issa kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=EmaTadashi en-aut-sei=Ema en-aut-mei=Tadashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=Boron kn-keyword=Boron en-keyword=Chirality kn-keyword=Chirality en-keyword=Circularly polarized luminescence kn-keyword=Circularly polarized luminescence en-keyword=Helical nanographenes kn-keyword=Helical nanographenes en-keyword=Ion sensing kn-keyword=Ion sensing END start-ver=1.4 cd-journal=joma no-vol=14 cd-vols= no-issue=37 article-no= start-page=4338 end-page=4343 dt-received= dt-revised= dt-accepted= dt-pub-year=2023 dt-pub=2023 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Catalytic synthesis and physical properties of CO2-based cross-linked poly(cyclohexene carbonate)s en-subtitle= kn-subtitle= en-abstract= kn-abstract=Bifunctional aluminum porphyrins (0.001 mol%) catalyzed the terpolymerization of cyclohexene oxide (CHO), bis(CHO), and CO2 to give cross-linked polycarbonates (CLPs) under solvent-free conditions. A small amount of bis(CHO) acted as a cross-linking agent, and the use of only 0.1 mol% bis(CHO) to CHO produced polymers of quite large sizes. The thermal and mechanical properties of CLPs could be altered by changing the structure and amount of bis(CHO), and the CLPs showed improved thermal stability and tensile strength as compared to linear poly(cyclohexene carbonate)s (PCHCs). The degradation of the CLPs was also investigated, and the selective cleavage of the cross-links was achieved by UV light irradiation to give linear PCHCs. The present study disclosed the potentials of cross-linking terpolymerization for the preparation of various CLPs with a constant CO2 content (31 wt%). en-copyright= kn-copyright= en-aut-name=MaedaChihiro en-aut-sei=Maeda en-aut-mei=Chihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KawabataKenta en-aut-sei=Kawabata en-aut-mei=Kenta kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NikiKaito en-aut-sei=Niki en-aut-mei=Kaito kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SakoYuma en-aut-sei=Sako en-aut-mei=Yuma kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=OkiharaTakumi en-aut-sei=Okihara en-aut-mei=Takumi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=EmaTadashi en-aut-sei=Ema en-aut-mei=Tadashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= affil-num=1 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=11 cd-vols= no-issue=22 article-no= start-page=5669 end-page=5675 dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=20200518 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Aluminum porphyrins with quaternary ammonium halides as catalysts for copolymerization of cyclohexene oxide and CO2: metal?ligand cooperative catalysis en-subtitle= kn-subtitle= en-abstract= kn-abstract=Bifunctional AlIII porphyrins with quaternary ammonium halides, 2-Cl and 2-Br, worked as excellent catalysts for the copolymerization of cyclohexene oxide (CHO) and CO2 at 120 ‹C. Turnover frequency (TOF) and turnover number (TON) reached 10?000 h?1 and 55?000, respectively, and poly(cyclohexene carbonate) (PCHC) with molecular weight of up to 281?000 was obtained with a catalyst loading of 0.001 mol%. In contrast, bifunctional MgII and ZnII counterparts, 3-Cl and 4-Cl, as well as a binary catalyst system, 1-Cl with bis(triphenylphosphine)iminium chloride (PPNCl), showed poor catalytic performances. Kinetic studies revealed that the reaction rate was first-order in [CHO] and [2-Br] and zero-order in [CO2], and the activation parameters were determined: ƒ’Hφ = 12.4 kcal mol?1, ƒ’Sφ = ?26.1 cal mol?1 K?1, and ƒ’Gφ = 21.6 kcal mol?1 at 80 ‹C. Comparative DFT calculations on two model catalysts, AlIII complex 2Œ and MgII complex 3Œ, allowed us to extract key factors in the catalytic behavior of the bifunctional AlIII catalyst. The high polymerization activity and carbonate-linkage selectivity originate from the cooperative actions of the metal center and the quaternary ammonium cation, both of which facilitate the epoxide-ring opening by the carbonate anion to form the carbonate linkage in the key transition state such as TS3b (ƒ’Hφ = 13.3 kcal mol?1, ƒ’Sφ = ?3.1 cal mol?1 K?1, and ƒ’Gφ = 14.4 kcal mol?1 at 80 ‹C). en-copyright= kn-copyright= en-aut-name=DengJingyuan en-aut-sei=Deng en-aut-mei=Jingyuan kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=RatanasakManussada en-aut-sei=Ratanasak en-aut-mei=Manussada kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=SakoYuma en-aut-sei=Sako en-aut-mei=Yuma kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=TokudaHideki en-aut-sei=Tokuda en-aut-mei=Hideki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=MaedaChihiro en-aut-sei=Maeda en-aut-mei=Chihiro kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=HasegawaJun-ya en-aut-sei=Hasegawa en-aut-mei=Jun-ya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=NozakiKyoko en-aut-sei=Nozaki en-aut-mei=Kyoko kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=EmaTadashi en-aut-sei=Ema en-aut-mei=Tadashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= affil-num=1 en-affil=Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo kn-affil= affil-num=2 en-affil=Institute for Catalysis, Hokkaido University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=6 en-affil=Institute for Catalysis, Hokkaido University kn-affil= affil-num=7 en-affil=Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo kn-affil= affil-num=8 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= END