Soluble, Highly Conjugated Polyenes via the Molybdenum-Catalyzed Copolymerization of Acetylene and Diethyl Dipropargylmalonate

Simple Synthesis of Poly(acetylene) Latex Particles in Aqueous Media

“…[7,8] Poly(acetylene)s obtained by cyclopolymerization display good solubility in common organic solvents such as benzene, toluene, dichloromethane, and chloroform, good long-term stability towards oxidation, and low energy transitions between the valence and conductivity bands. [7][8][9][10] They can be synthesized by using Ziegler catalysts, [11,12] Pd catalysts, [13] anionic polymerization, [14] or binary/ternary Mo or W catalysts. [15] Well-defined molybdenum carbenes in high oxidation states (Schrock catalysts I, Figure 1) must be regarded as superior since they cyclopolymerize 1,6-heptadiynes in a living manner [15,16] and can be tuned so that only one single repeat unit, for example, 1,3-(cyclopent-1-enylene)vinylenes [17,18] or 1,3-(cyclohexen-1-enylene)methylidenes, [9,10] is obtained.…”

“…[7][8][9][10] They can be synthesized by using Ziegler catalysts, [11,12] Pd catalysts, [13] anionic polymerization, [14] or binary/ternary Mo or W catalysts. [15] Well-defined molybdenum carbenes in high oxidation states (Schrock catalysts I, Figure 1) must be regarded as superior since they cyclopolymerize 1,6-heptadiynes in a living manner [15,16] and can be tuned so that only one single repeat unit, for example, 1,3-(cyclopent-1-enylene)vinylenes [17,18] or 1,3-(cyclohexen-1-enylene)methylidenes, [9,10] is obtained. Despite their unique catalytic properties, the strictly air-and moisture-free conditions that are required for the use of Schrock catalysts are a major limitation to technically relevant applications.…”

Eine einfache Synthese von Polyacetylen‐Latices in wässrigem Medium

“…[7,8] Durch Cyclopolymerisation hergestellte Polyacetylene sind in gängigen organischen Lösungsmitteln wie Benzol, Toluol, Dichlormethan oder Chloroform gut löslich, zeigen eine gute Langzeitstabilität gegen Sauerstoff und weisen kleine Energiedifferenzen zwischen dem Valenz-und Leitungsband auf. [7][8][9][10] Prinzipiell können sie mithilfe von Ziegler-Katalysatoren, [11,12] Pd-Katalysatoren, [13] durch an-ionische Polymerisation [14] oder mithilfe binärer/ternärer Mooder W-Katalysatoren hergestellt werden. [15] Definierte Molybdäncarbene mit hoher Oxidationsstufe (Schrock-Katalysatoren I; Abbildung 1) gelten bis jetzt als die besten Systeme, da sie 1,6-Heptadiine lebend polymerisieren [15,16] und überdies so verändert werden können, dass selektiv eine einzige Repetiereinheit, z.…”

“…B. 1,3-(Cyclopent-1-enylen)vinylene [17,18] oder 1,3-(Cyclohexen-1-enylen)methylidene, [9,10] [RuCl 2 ( = CH-(2-(2-PrO)-C 6 H 4 ))(1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolin-2-yliden)], III, IV) [19] sind luft-und feuchtigkeitsbeständige Katalysatoren mit bemerkenswerter Aktivität, die in manchen Fällen sogar die der hoch aktiven Schrock-Katalysatoren erreicht. [20] Unge- 2 …”

Twisting poly(3-substituted thiophene)s: cyclopolymerization of gemini thiophene monomers through catalyst-transfer polycondensation

“…We can then deduce that the dihedral angle of P3XT is dictated by the size of the macrocycles formed (Scheme 1b). To date, cyclopolymerization that produces π-conjugated polymers has been limited to the synthesis of polyacetylene by ring-closing metathesis; [24][25][26] to the best of our knowledge, this study is the first report of polythiophene synthesis through cyclopolymerization. Japan).…”