Discrete Cyclic Polymers with Uniform Chain Length

Macromolecules, Год журнала: 2024, Номер unknown

Опубликована: Сен. 20, 2024

Язык: Английский

---

C–H/C–H Oxidative Direct Arylation Polycondensation to Isoindigo-Based n-Type Conjugated Polymers

Macromolecules, Год журнала: 2024, Номер 57(9), С. 4158 - 4166

Опубликована: Апрель 24, 2024

Two high molecular weight conjugated polymers (CPs), i.e., poly[N,N′-bis(4-tetradecyloctadecyl)-7,7′-difluoroisoindigo-alt-2,2′-bithiazole] (P2FI2Tz) and poly[N,N′-bis(4-tetradecyloctadecyl)-5,5′,7,7′-tetrafluoroisoindigo-alt-2,2′-bithiazole] (P4FI2Tz), were synthesized via C–H/C–H oxidative direct arylation polycondensation (Oxi-DArP) using PdCl2/CuCl/Cu(OAc)2 as catalytic system chlorobenzene solvent. Both are unipolar n-type semiconductors with electron mobility (μe) > 0.2 cm2 V–1 s–1, attributed to their low-lying highest occupied orbitals (HOMOs) lowest unoccupied orbital (LUMOs), which −6.01/–3.69 −6.24/–3.82 eV for P2FI2Tz P4FI2Tz, respectively. was also C–Br/C–H (DArP) Stille polycondensation. The resultant P2FI2Tz-D P2FI2Tz-S showed slightly lower μe compared Oxi-DArP-made polymer (P2FI2Tz-O1) a similar weight. Notably, Oxi-DArP is much faster more efficient than DArP number-average (Mn) above 40 kDa, obtained in 9 h of Oxi-DArP, significantly shorter 24 Mn 191 kDa could be by extending the polymerization time 16 h. Our results prove an protocol synthesize semiconductors. This first comparative study on three methods, DArP,

Язык: Английский

---

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers

Angewandte Chemie, Год журнала: 2023, Номер 135(50)

Опубликована: Ноя. 7, 2023

Abstract In contrast to edge‐on and face‐on orientations, end‐on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due sluggishly thermodynamic equilibrium states. Herein, we report programmatic pathway fabricate nanoarchitectonics on metallopolymers by surface‐initiated simultaneous electrosynthesis assembly. Self‐assembled monolayer (SAM) with bottom‐up oriented electroactive molecules as temple allows orientation, stacking, reactive addition monomers triggered switching alternative redox reactions well crystallization small molecules. Repeating same reaction can repair unreactive site SAM dynamically statistically ensure maximum iterative coverage ideal linear coefficients between optical or electrical responses times. The resulting uniaxially assembled over centimeter‐sized areas subnanometer‐uniform morphology exhibit ultrahigh modulus an inorganic indium tin oxides highest conductance among molecular monolayers. Their memristive devices provide quantitative function length, bias, junctions. Precise processing electrically assisted assembly printing technique present sophisticated optoelectric functions dimensional batch‐to‐batch consistency for micro‐sized organic materials electronics.

Язык: Английский

---

Single-component organic solar cells—Perspective on the importance of chemical precision in conjugated block copolymers

Frontiers in Chemistry, Год журнала: 2023, Номер 11

Опубликована: Дек. 12, 2023

Organic photovoltaics (OPV) present a promising thin-film solar cell technology with particular benefits in terms of weight, aesthetics, transparency, and cost. However, despite being studied intensively since the mid 90's, OPV has not entered mass consumer market yet. Although efficiency gap other largely been overcome, active layer stability performance reproducibility issues have fully resolved. State-of-the-art devices employ physical mixture electron donor acceptor molecules bulk heterojunction layer. These blends are prone to morphological changes, leading losses over time. On hand, "single-component" organic cells, constituents chemically connected within single material, preventing demixing thereby enhancing device stability. Novel single-component materials affording reasonably high efficiencies improved lifetimes recently emerged. In particular, combination structures conjugated block copolymers (CBCs) presents an exciting approach. Nevertheless, current CBCs poorly defined from structural point view, while synthetic protocols remain unoptimized. More controlled synthesis followed by proper analysis is, however, essential develop rational structure-property-device relations drive field forward. this perspective, we provide short overview state-of-the-art cells prepared CBCs, reflect on their troublesome characterization importance chemical precision these structures, give some recommendations, discuss potential impact aspects field.

Язык: Английский

---

Backbone Engineering and Side Group Manipulation in Covalent Organic Frameworks for Overall Solar-Driven Hydrogen Peroxide Production

Giant, Год журнала: 2024, Номер 20, С. 100335 - 100335

Опубликована: Авг. 23, 2024

Covalent Organic Frameworks (COFs) have emerged as highly promising materials for the photocatalytic production of hydrogen peroxide (H2O2) due to their exceptional structural tunability, robust frameworks, and high porosity. The efficient overall photosynthesis H2O2 hinges on simultaneous occurrence oxygen reduction reaction (ORR) water oxidation (WOR). This review introduces recent progress in developing key approaches such backbone engineering incorporation side groups facilitate these critical pathways. For example, innovative COF designs, spatially separating redox centers, demonstrated significant improvements performance. Moreover, introduction thioether-decorated triazine-based COFs hexavalent triphenylene knots has led remarkable rates. Furthermore, this also addresses challenges associated with practical implementation COFs, including stability under operational conditions necessity reactor designs. future prospects sustainable chemical synthesis are discussed, emphasizing potential revolutionize through green methodologies. aims provide valuable insights into design development high-performance photocatalysts, paving way applications value-added chemicals.

Язык: Английский

---

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(50)

Опубликована: Ноя. 7, 2023

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due sluggishly thermodynamic equilibrium states. Herein, we report programmatic pathway fabricate nanoarchitectonics on metallopolymers by surface-initiated simultaneous electrosynthesis assembly. Self-assembled monolayer (SAM) with bottom-up oriented electroactive molecules as temple allows orientation, stacking, reactive addition monomers triggered switching alternative redox reactions well crystallization small molecules. Repeating same reaction can repair unreactive site SAM dynamically statistically ensure maximum iterative coverage ideal linear coefficients between optical or electrical responses times. The resulting uniaxially assembled over centimeter-sized areas subnanometer-uniform morphology exhibit ultrahigh modulus an inorganic indium tin oxides highest conductance among molecular monolayers. Their memristive devices provide quantitative function length, bias, junctions. Precise processing electrically assisted assembly printing technique present sophisticated optoelectric functions dimensional batch-to-batch consistency for micro-sized organic materials electronics.

Язык: Английский

---

Modular Synthesis of Conjugated Aromatic Boronate Esters by Radical Xanthate Addition

Synthesis, Год журнала: 2024, Номер 56(13), С. 2066 - 2076

Опубликована: Апрель 25, 2024

Abstract Conjugated aromatic boronate esters serve as crucial intermediates in the synthesis of pharmaceuticals and polymer materials. Traditional methods for their typically involve organoboration ring compounds, where pre-constructions rings are required. Here, we present a general strategy diverse conjugated based on radical addition xanthates. Through this method, synthesized various ester xanthates that could be utilized platform to furnish building blocks, including thiophenes, pyrroles, tetralones, naphthols, naphthylamines. This cost-effective holds promise viable method industrial-scale production (hetero)aromatic esters.

Язык: Английский

---

Exploring the reactivity and interactions of a poly(fluorene‐co‐tetrazine)‐conjugated polymer with Single‐walled Carbon Nanotubes

Journal of Polymer Science, Год журнала: 2024, Номер unknown

Опубликована: Сен. 17, 2024

Abstract Conjugated tetrazine‐containing polymers that undergo inverse electron demand Diels‐Alder (IEDDA) reactions with trans ‐cyclooctenes are interesting not only for their intrinsic optoelectronic properties, but also interactions π‐conjugated surfaces. Here, we prepared a series of poly(fluorene‐ co ‐tetrazine) and carried out IEDDA to decorate them hydroxyl, hexadecyl, or triethylene glycol side chains. The were investigated pre‐ post‐IEDDA coupling in terms ability disperse single‐walled carbon nanotubes (SWNTs) organic solvent. It was found polymer molecular weight, chain structure, degree conjugation all impacted the quality SWNT dispersions. While starting produced concentrated dispersions, containing dihydropyridazine groups did produce dispersions equal concentration. However, upon oxidation fully aromatic pyridazines, regained form Furthermore, exhibited increased selectivity toward metallic SWNTs relative polymer. Due efficiency reaction, it possible use this chemistry derivatize nanotube complex post‐dispersion. Overall, work demonstrates first reactive polytetrazines SWNTs, allowing rapid modification polymer‐nanotube complexes.

Язык: Английский

---

Investigation of electrochemical, optical, and thermal properties via oligomerization of aminophenol monomer containing halogen and nitro groups using two distinct oxidants

Reactive and Functional Polymers, Год журнала: 2023, Номер 193, С. 105771 - 105771

Опубликована: Ноя. 5, 2023

Язык: Английский

---