Efficient Conversion of Inert Nitriles to Multifunctional Poly(5-amino-1,2,3-triazole)s via Regioselective Click Polymerization with Azide Monomers under Ambient Conditions

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 6652 - 6664

Опубликована: Фев. 29, 2024

Nitrile compounds are abundant, stable, cheap, and readily available natural chemical industrial sources. However, the efficient conversion of nitrile monomers to functional polymers is mostly limited due their inert reactivity, developing polymerizations based on under very mild conditions still a big challenge. In this work, facile powerful base-catalyzed acetonitrile-azide click polymerization was successfully established ambient conditions. This also enjoys merits short reaction time (15 min), 100% atom economy, transition-metal-free catalyst system, regioselectivity. A series poly(5-amino-1,2,3-triazole)s (PATAs) with high weight-average molecular weights (Mw, up 204,000) were produced in excellent yields (up 99%). The PATAs containing tetraphenylethene (TPE) moieties exhibit unique aggregation-induced emission (AIE) characteristics, which could be used sensitively detect Fe(III) ions low limit detection (1.205 × 10–7 M) specifically image lysosomes living cells. Notably, facilely post-modified primary amino groups polymer chains even through one-pot tandem reaction. Thus, work not only establishes new convert stable nitriles but generates versatile properties for diverse applications.

Язык: Английский

---

Water‐Involved Carbon‐Nitrogen Triple‐Bond Monomer Based Polymerization toward Processable Functional Polyamides under Ambient Conditions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(44)

Опубликована: Авг. 6, 2024

Polyamide plays a pivotal role in engineering thermoplastics. Constrained by the harsh conditions and arduous procedures for its industrial synthesis, developing facile synthesis of polyamides is still challengeable holds profound significance. Herein, we successfully utilized water as one monomers to synthesize functional under ambient conditions. A powerful multicomponent polymerization water, isocyanides, chlorooximes was established phosphate-buffered saline. Soluble thermally stable with high weight-average molecular weights (up 53 900) were obtained excellent yields 95 %). The exhibits unique polymerization-induced emission characteristics, converting non-emissive into unconventional emissive polymers. Notably, resultant could undergo effective post-modification via hydroxyl-yne click reaction. By incorporating various groups polyamide, color be fine-tuned from blue green red. Remarkably, refractive index (n) polyamide at 589 nm increased 1.6173 1.7227 Δn unprecedentedly 0.1054 non-heavy atom-containing polymers after post-modification, micron-thick films exhibited transparency visible region. Thus, this work not only establishes toward novel but also opens up an avenue their versatile functionalization.

Язык: Английский

---

Ethynyl-Directed Dual C(sp³)–H Activation Polymerization to Construct Regio- and Stereoregular C(sp³)–C(sp³) Bond Polymers

Macromolecules, Год журнала: 2023, Номер 57(1), С. 122 - 131

Опубликована: Дек. 20, 2023

The establishment of facile, efficient, and precise synthetic approaches to selectively convert stable C–H bonds functional polymers has great significance in both chemistry material science especially by C(sp3)–H activation. Here, an efficient dual activation polymerization alkynes activated methylenes catalyzed Pd(PPh3)4/benzoic acid was successfully established with a 100% atom economy excellent regio- stereoselectivity. A series high-weight-average molecular-weight (Mw approximately 66,500) poly(aryl butene)s (PABs) sole E configuration were generated remarkable yields (approximately 99%). PABs exhibit good thermal stability, solubility, film-forming ability. In addition, the thin PAB films display high refractive indices (RI) up 1.7126 at 589 nm. Because this strong group tolerance, luminophores can be readily constructed into main chain empower multicolored luminescence various states. Notably, containing tetraphenylethene (TPE) moiety feature unique aggregation-induced emission (AIE) peculiarities, which could specifically sensitively detect Fe(III) ions low limit detection (LOD) 1.585 × 10–6 M.

Язык: Английский

---

Water‐Involved Carbon‐Nitrogen Triple‐Bond Monomer Based Polymerization toward Processable Functional Polyamides under Ambient Conditions

Angewandte Chemie, Год журнала: 2024, Номер 136(44)

Опубликована: Авг. 6, 2024

Abstract Polyamide plays a pivotal role in engineering thermoplastics. Constrained by the harsh conditions and arduous procedures for its industrial synthesis, developing facile synthesis of polyamides is still challengeable holds profound significance. Herein, we successfully utilized water as one monomers to synthesize functional under ambient conditions. A powerful multicomponent polymerization water, isocyanides, chlorooximes was established phosphate‐buffered saline. Soluble thermally stable with high weight‐average molecular weights (up 53 900) were obtained excellent yields 95 %). The exhibits unique polymerization‐induced emission characteristics, converting non‐emissive into unconventional emissive polymers. Notably, resultant could undergo effective post‐modification via hydroxyl‐yne click reaction. By incorporating various groups polyamide, color be fine‐tuned from blue green red. Remarkably, refractive index ( n ) polyamide at 589 nm increased 1.6173 1.7227 Δ unprecedentedly 0.1054 non‐heavy atom‐containing polymers after post‐modification, micron‐thick films exhibited transparency visible region. Thus, this work not only establishes toward novel but also opens up an avenue their versatile functionalization.

Язык: Английский

---