Polyarylcyanation of Diyne: A One-Pot Three-Component Convenient Route for <i>In Situ</i> Generation of Polymers with AIE Characteristics

A facile, one-pot, three-component polymerization route for <i>in situ</i> generation of polymers with aggregation-induced emission (AIE) characteristics was developed. The polycoupling of dibromoarenes, internal diynes and potassium ferrocyanide was catalyzed by palladium acetate and sodium bicarbonate and proceeded smoothly in dimethylacetamide under nitrogen at 120 °C, producing poly­(triphenylacrylonitrite)­s (PTPANs) with high weight-average molecular weights of up to 223000 in high yields of up to 84%. This polymerization method enjoys the remarkable advantages of high reaction rate and efficiency and broad monomer scope. Model reaction was carried out to aid the structure characterization and property investigation of the obtained polymers. All the polymers show remarkable thermal stability, losing merely 5% of their weight at high temperature of up to 513 °C. They are soluble in common organic solvents and their spin-coated thin films exhibit high refractive indices (1.6482–1.7682). Thanks to the triphenylethene chromophore <i>in situ</i> generated during the polymerization, all the polymers are AIE-active and show strong light emission in the solid state. While UV irradiation of the polymer thin films in air through upper masks photo-oxidizes the exposed parts and quenches their light emission, the unexposed parts remain emissive. Two-dimensional fluorescent patterns with good resolution are thus generated

Polyarylcyanation of Diyne: A One-Pot Three-Component Convenient Route for <i>In Situ</i> Generation of Polymers with AIE Characteristics

A facile, one-pot, three-component polymerization route for <i>in situ</i> generation of polymers with aggregation-induced emission (AIE) characteristics was developed. The polycoupling of dibromoarenes, internal diynes and potassium ferrocyanide was catalyzed by palladium acetate and sodium bicarbonate and proceeded smoothly in dimethylacetamide under nitrogen at 120 °C, producing poly­(triphenylacrylonitrite)­s (PTPANs) with high weight-average molecular weights of up to 223000 in high yields of up to 84%. This polymerization method enjoys the remarkable advantages of high reaction rate and efficiency and broad monomer scope. Model reaction was carried out to aid the structure characterization and property investigation of the obtained polymers. All the polymers show remarkable thermal stability, losing merely 5% of their weight at high temperature of up to 513 °C. They are soluble in common organic solvents and their spin-coated thin films exhibit high refractive indices (1.6482–1.7682). Thanks to the triphenylethene chromophore <i>in situ</i> generated during the polymerization, all the polymers are AIE-active and show strong light emission in the solid state. While UV irradiation of the polymer thin films in air through upper masks photo-oxidizes the exposed parts and quenches their light emission, the unexposed parts remain emissive. Two-dimensional fluorescent patterns with good resolution are thus generated

Synthesis of Functional Poly(propargyl imine)s by Multicomponent Polymerizations of Bromoarenes, Isonitriles, and Alkynes

Here we reported a versatile and multicomponent polymerization (MCP) approach that enabled the synthesis of functional poly­(propargyl imine)­s with well-defined structures and high molecular weight (<i>M</i>_w up to 38 200) in excellent yields (up to 93%) from readily accessible monomers of dibromoarenes, isonitriles, and diynes. This MCP had the advantages of simple operation, wide substrate scope, and mild reaction conditions. The resulting polymers possessed good solubility and showed high thermal stability and refractive indices. The tetraphenylethene-containing polymer displayed a phenomenon of aggregation-induced emission and could respond to various acidic vapors

Regio- and stereoselective polymerization of diynes with inorganic comonomer: a facile strategy to conjugated poly(p-arylene dihalodiene)s with processability and postfunctionalizability

Copyright © 2018 American Chemical Society. Development of new methodologies for synthesizing polymers with novel structures and unique properties is a fundamentally important area in polymer science. Herein, a novel synthetic strategy to conjugated poly(p-arylene dihalodiene)s (PADs) with high regio- and stereoselectivity was developed. In the presence of PdBr 2 and CuBr 2 , the polymerizations of terminal alkynes proceeded smoothly in air without heating to generate PADs in high yields (up to 95.3%) with high molecular weights (M w up to 915 900). Low-cost inorganic CuBr 2 played dual roles as cocatalyst and comonomer. The PADs possessed good solubility and film-formi ng ability. Their thin films exhibited high refractive indices (1.7149-1.7245) and would be fabricated into well-resolved fluorescent photopatterns by photolithography. Thanks to the vinyl bromine functionality, the PADs could undergo efficient postmodification to afford polymers with more sophisticated structures and applications.

Hydrogenation of Hexa-<i>peri</i>-hexabenzocoronene: An Entry to Nanographanes and Nanodiamonds

The fabrication of atomically precise nanographanes is a largely unexplored frontier in carbon-sp3 nanomaterials, enabling potential applications in phononics, photonics and electronics. One strategy is the hydrogenation of prototypical nanographene monolayers and multilayers under vacuum conditions. Here, we study the interaction of atomic hydrogen, generated by a hydrogen source and hydrogen plasma, with hexa-peri-hexabenzocoronene on gold using integrated time-of-flight mass spectrometry, scanning tunneling microscopy and Raman spectroscopy. Density functional tight-binding molecular dynamics is employed to rationalize the conversion to sp3 carbon atoms. The resulting hydrogenation of hexa-peri-hexabenzocoronene molecules is demonstrated computationally and experimentally, and the potential for atomically precise hexa-peri-hexabenzocoronene-derived nanodiamond fabrication is proposed

SI files for "Regio- and stereoselective polymerization of diynes with inorganic comonomer: A facile strategy to conjugated poly(p-arylene dihalodiene)s with processability and postfunctionalizability"

These are the SI files for "Regio- and stereoselective polymerization of diynes with inorganic comonomer: A facile strategy to conjugated poly(p-arylene dihalodiene)s with processability and postfunctionalizability".Abstract for associated article:Development of new methodologies for synthesizing polymers with novel structures and unique properties is a fundamentally important area in polymer science. Herein, a novel synthetic strategy to conjugated poly(p-arylene dihalodiene)s (PADs) with high regio- and stereoselectivity was developed. In the presence of PdBr 2 and CuBr 2 , the polymerizations of terminal alkynes proceeded smoothly in air without heating to generate PADs in high yields (up to 95.3%) with high molecular weights (M w up to 915 900). Low-cost inorganic CuBr 2 played dual roles as cocatalyst and comonomer. The PADs possessed good solubility and film-formi ng ability. Their thin films exhibited high refractive indices (1.7149-1.7245) and would be fabricated into well-resolved fluorescent photopatterns by photolithography. Thanks to the vinyl bromine functionality, the PADs could undergo efficient postmodification to afford polymers with more sophisticated structures and applications.</div

Hydrogenation of Hexa-<i>peri</i>-hexabenzocoronene: An Entry to Nanographanes and Nanodiamonds

The fabrication of atomically precise nanographanes is a largely unexplored frontier in carbon-sp3 nanomaterials, enabling potential applications in phononics, photonics and electronics. One strategy is the hydrogenation of prototypical nanographene monolayers and multilayers under vacuum conditions. Here, we study the interaction of atomic hydrogen, generated by a hydrogen source and hydrogen plasma, with hexa-peri-hexabenzocoronene on gold using integrated time-of-flight mass spectrometry, scanning tunneling microscopy and Raman spectroscopy. Density functional tight-binding molecular dynamics is employed to rationalize the conversion to sp3 carbon atoms. The resulting hydrogenation of hexa-peri-hexabenzocoronene molecules is demonstrated computationally and experimentally, and the potential for atomically precise hexa-peri-hexabenzocoronene-derived nanodiamond fabrication is proposed

Regio- and Stereoselective Polymerization of Diynes with Inorganic Comonomer: A Facile Strategy to Conjugated Poly(<i>p</i>‑arylene dihalodiene)s with Processability and Postfunctionalizability

Development of new methodologies for synthesizing polymers with novel structures and unique properties is a fundamentally important area in polymer science. Herein, a novel synthetic strategy to conjugated poly­(<i>p</i>-arylene dihalodiene)­s (PADs) with high regio- and stereoselectivity was developed. In the presence of PdBr₂ and CuBr₂, the polymerizations of terminal alkynes proceeded smoothly in air without heating to generate PADs in high yields (up to 95.3%) with high molecular weights (<i>M</i>_w up to 915 900). Low-cost inorganic CuBr₂ played dual roles as cocatalyst and comonomer. The PADs possessed good solubility and film-forming ability. Their thin films exhibited high refractive indices (1.7149–1.7245) and would be fabricated into well-resolved fluorescent photopatterns by photolithography. Thanks to the vinyl bromine functionality, the PADs could undergo efficient postmodification to afford polymers with more sophisticated structures and applications

Blood Circulation Assessment by Steadily Fluorescent Near-Infrared-II Aggregation-Induced Emission Nano Contrast Agents

The dysfunction of the blood circulation system typically induces acute or chronic ischemia in limbs and vital organs, with high disability and mortality. While conventional tomographic imaging modalities have shown good performance in the diagnosis of circulatory diseases, multiple limitations remain for real-time and precise hemodynamic evaluation. Recently, fluorescence imaging in the second region of the near-infrared (NIR-II, 1000–1700 nm) has garnered great attention in monitoring and tracing various biological processes in vivo due to its advantages of high spatial–temporal resolution and real-time feature. Herein, we employed NIR-II imaging to carry out a blood circulation assessment by aggregation-induced emission fluorescent aggregates (AIE nano contrast agent, AIE NPs). Thanks to the longer excited wavelength, enhanced absorptivity, higher brightness in the NIR-II region, and broader optimal imaging window of the AIE NPs, we have realized a multidirectional assessment for blood circulation in mice with a single NIR-II imaging modality. Thus, our work provides a fluorescence contrast agent platform for accurate hemodynamic assessment

Blood Circulation Assessment by Steadily Fluorescent Near-Infrared-II Aggregation-Induced Emission Nano Contrast Agents

The dysfunction of the blood circulation system typically induces acute or chronic ischemia in limbs and vital organs, with high disability and mortality. While conventional tomographic imaging modalities have shown good performance in the diagnosis of circulatory diseases, multiple limitations remain for real-time and precise hemodynamic evaluation. Recently, fluorescence imaging in the second region of the near-infrared (NIR-II, 1000–1700 nm) has garnered great attention in monitoring and tracing various biological processes in vivo due to its advantages of high spatial–temporal resolution and real-time feature. Herein, we employed NIR-II imaging to carry out a blood circulation assessment by aggregation-induced emission fluorescent aggregates (AIE nano contrast agent, AIE NPs). Thanks to the longer excited wavelength, enhanced absorptivity, higher brightness in the NIR-II region, and broader optimal imaging window of the AIE NPs, we have realized a multidirectional assessment for blood circulation in mice with a single NIR-II imaging modality. Thus, our work provides a fluorescence contrast agent platform for accurate hemodynamic assessment