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Multicolor emission from non-conjugated polymers based on a single switchable boron chromophore
摘要： Multicolor emissive and responsive materials are highly attractive due to their potential applications in various fields, and polymers are preferred for their good processability and high stability. Herein, we report a series of new polymers based on a methacrylate monomer containing a switchable boron chromophore. In spite of the unconjugated nature, interestingly, the homopolymers from this monomer display rare multicolor fluorescence in solution that is highly dependent on the degree of polymerization (DP). With an ascending DP, the local concentration of the chromophore increases, leading to a higher propensity for switching the blue emitting tricoordinate boron chromophore to the red emitting tetracoordinate one. The homopolymers also display temperature and solvent-dependent emission colour change. Furthermore, pure white-light emission could be achieved in various solvents by precisely tuning the homopolymer molecular weight, or in films/solid state by copolymerizing the emissive boron monomer with non-emissive monomers in an appropriate ratio.
关键词： Multi-responsiveness,Non-conjugated Polymer,Single Chromophore,White Light Emission,Multicolor Emission
更新于2025-09-10 09:29:36
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Water-Dispersed Conjugated Polyelectrolyte for Visible-Light Hydrogen Production
摘要： Conjugated polymer-based photocatalysts have shown great potential in H2 production via water splitting, but an intrinsic drawback of conventional hydrophobic polymer photocatalysts is their poor wettability and relatively large particle size in aqueous media, which is favorable for charge recombination with limited interfacial reaction efficiency. Herein, a well-dispersed organic water reduction system using cationic conjugated polyelectrolyte as the photocatalyst has been reported for the first time. In comparison to a model polymer (PFBT) bearing the same conjugated backbone, the polyelectrolyte exhibits significantly enhanced photocatalytic efficiency due to the extended light absorption and improved charge separation of the polymer aggregates.
关键词： conjugated polyelectrolyte,water-dispersed,visible-light hydrogen production
更新于2025-09-10 09:29:36
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Enhanced electrochromic performances of Polythieno[3,2-b]thiophene with multicolor conversion via embedding EDOT segment
摘要： A heterocyclic oligomer, thieno[3,2-b]thiophene (TT) end-capped famous 3,4-ethylenedioxythiophene (EDOT) unit and their electrosynthesized polymer P(TT-EDOT-TT) have been facilely achieved. To in-depth understand the effects of structural modification on physico-chemical properties and electrochromic performances of monomers and/or polymers, the absorption spectroscopy, electrochemistry, micromorphology, and spectro-electrochemistry were systematically studied. In contrast to TT and EDOT, TT-EDOT-TT possessed extended π-conjugation and narrowed band gap in molecular level. Through carefully comparison with PTT, it has been found that the electrochromic performances of P(TT-EDOT-TT) film exhibited much higher optical contrast (69%, while 3% for PTT in the near-infrared region) and superior coloring efficiency (255.3 cm2 C?1, while 36.8 cm2 C?1 for PTT), and switching times (within 1 s, while more than 9 s for PTT). Notably, P(TT-EDOT-TT) film can achieve the mutual conversion between RGB primary colors (red–green–blue) under variable voltages, which hold quite promising for display applications.
关键词： Conjugated polymers,Polythieno[3,2-b]thiophene,Electrochromism
更新于2025-09-10 09:29:36
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Investigation of hydrogen-bonding mediated molecular packing of diketopyrrolopyrrole based donor-acceptor oligomers in the solid state
摘要： Two diketopyrrolopyrrole (DPP)-based Donor-Acceptor oligomers with thermal labile 2-methylhexyl-2-oxylcarbonyl (mHoc) groups, mHocPBT and mHocTBT, were synthesized and characterized to study the hydrogen-bonding mediated molecular packing in solid state. The soluble oligomers can be converted to strong intermolecular hydrogen-bonded and pigment-like materials HPBT and HTBT by annealing the casted solid film at a temperature between 180 and 200 °C. The formation of intermolecular hydrogen bonding significantly altered the conformation of the molecules, molecular packing structure and related optical properties of the oligomers, with HPBT molecule exhibiting bathochromic shift and HTBT molecule exhibiting hypsochromic shift on UV/Vis spectra. Spin-casted mHocTBT and HTBT films also exhibited interesting morphology and charge transport properties. Even though the single mHocTBT oligomer molecule has a better coplanar molecular conformation as compared with that of HTBT, an enhanced π-π stacking structure and larger crystal grain size rendered HTBT film better charge transport performance.
关键词： Molecular Packing,Conjugated Molecules,Hydrogen Bond
更新于2025-09-10 09:29:36
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Synthesis, characterization, and self-assembly behavior of poly(m-phenylene)s with terthiophene and chiral side chains
摘要： A series of novel poly(m-phenylene)s with terthiophene and/or chiral side chains have been developed to investigate the correlation between poly(m-phenylene) polymer structure and self-assembly behaviors. As a result of circular dichroism spectroscopy, a poly(m-phenylene) that alternately had terthiophene and chiral side chains exhibited the clear Cotton effect in THF, THF/methanol, and THF/acetonitrile conditions, indicating that the defined nanostructure was successfully formed by efficiently using the two interactions between side chains even in the good solvent condition. On the other hand, poly(m-phenylene)s with an irregularly sequence of terthiophene and chiral side chains did not have a capability to form the nanostructure regardless of solvent condition. These results demonstrated that an efficient usage of side chain interactions based on an alternating polymer structure was important for the formation of self-assembled nanostructure in poly(m-phenylene)s.
关键词： Self-assembly,Circular dichroism,Conjugated polymer,Polyphenylene
更新于2025-09-10 09:29:36
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Ultrathin 2D Conjugated Polymer Nanosheets for Solar Fuel Generation
摘要： Two-dimensional (2D) polymers are fascinating as they exhibit unique physical, chemical, mechanical, and electronic properties that are completely different from those of traditional linear or branched polymers. They are very promising for applications in catalysis, separation, optoelectronics, energy storage, and nanomedicine. Recently, ultrathin 2D conjugated polymers have emerged as advanced materials for converting solar energy into chemical energy. The inherent 2D planar structure with in-plane periodicity offers many features that are highly desirable for photon-involved catalytic energy conversion processes, including high absorption coefficients, large surface areas, abundant surface active sites, and efficient charge separation. Moreover, the possibility of finely tuning the optoelectronic and structural properties through precise molecular engineering has opened up new opportunities for design and synthesis of novel 2D polymer nanosheets with unprecedented applications. Herein, we highlight recent advances in developing ultrathin 2D conjugated polymer nanosheets for solar-to-chemical energy conversion. Specifically, we discuss emerging applications of ultrathin 2D conjugated polymer nanosheets for solar-driven water splitting and CO2 reduction. Meanwhile, future challenges and prospects for design and synthesis of ultrathin 2D conjugated polymer nanosheets for solar fuel generation are also included.
关键词： Energy conversion,2D polymers,Nanosheets,Conjugated polymers,Photocatalysis
更新于2025-09-10 09:29:36
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π-Dimerization ability of conjugated oligomer dication diradicaloids composed of dithienylpyrrole and benzodithiophene units
摘要： 2+ composed of 2,5- di(2- thienyl)- N- 2+ and 2 Stable conjugated oligomer dications 1 methylpyrrole (DTP) units at the both ends of the π- systems with methoxy substitu- ents at the 3- position of thienyl units and methylthio end- capping group and benzo[2,1- b:3,4- b′]dithiophene (BDT) unit(s) at the central part with sterically de- manding phenyl substituents were synthesized. From DFT calculations and ESR ex- 2+ was reduced periments, it was concluded that the diradical character in 1 in comparison with the radical character of their reference compound 3·+ composed 2+ was considered to have a of one DTP and one BDT units. In addition, the shorter 1 2+. Nevertheless, judging from the re- further lower diradical character than that of 2 2+ showed a comparable π- 2+ and 2 sults of VT- UV- vis- NIR measurements, both 1 dimerization ability at the DTP moiety in dichloromethane solution with 3·+.
关键词： dithienylpyrrole,diradicaloids,conjugated oligomer dications,benzodithiophene,π- Dimerization
更新于2025-09-10 09:29:36
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Magnetic field effect on polaron recombination in conjugated polymers
摘要： By using the one-dimensional tight-binding model, we theoretically investigate the effect of magnetic field on the collision of the oppositely charged polarons with their spin antiparallel in cis-polyacetylene. We adopt the non-adiabatic approach to simulate the dynamical evolution of polaron spin. Under the effect of electric field with a moderate strength, the polarons initially localized at the chain-end of polyacetylene move towards each other. During the collision process, an obvious spin precession is obtained, and the precession period is found to be inversely proportional to the strength of magnetic field. While after including electron-electron interaction in form of Hubbard model, the period is no longer constant. With the decrease of distance between the oppositely charged polarons, the precession of their spin slows down. We also find that there is a critical value of electron-electron interaction strength, over which the spin precession of polaron disappears. In addition, we demonstrate that under the effect of magnetic field, the polarons could recombine or pass through each other to form the singlet exciton, rather than be dissociated after collision between them with the strong electron-electron interaction, and then the electroluminescence efficiency of organic optoelectronic devices is improved.
关键词： polaron,conjugated polymer,Zeeman effect,electron-electron interaction,spin precession,magneto-electroluminescence
更新于2025-09-10 09:29:36
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Stretchable Conjugated Polymers: A Case Study in Topic Selection for New Research Groups
摘要： The field of π-conjugated (semiconducting) polymers has been underwritten largely because of the promise of flexible (and increasingly, stretchable) devices for energy and health care. Our research group has spent much of the past six years studying the mechanical properties of conjugated polymers. Mechanically robust materials can extend the life spans of devices such as solar cells and organic light-emitting diode (OLED) panels and enable high throughput processing techniques such as roll-to-roll printing. Additionally, wearable and implantable devices, including electronic skin, implantable pressure sensors, and haptic actuators, benefit by having moduli and extensibilities close to those of biological tissue. At the time of our laboratory’s inception, however, the optoelectronic properties of conjugated polymers were understood in much greater depth than their mechanical properties. We therefore set out, as our laboratory’s first research topic, to understand the molecular and microstructural determinants of the mechanical properties of conjugated polymers. This is an Account not only of our scientific findings but also of the pragmatic aspects, including personnel, funding, and time constraints, behind our studies as a nascent research group. We hope that this Account will provide information to newly independent scientists about the process of starting a new research laboratory.
关键词： π-conjugated polymers,stretchable electronics,organic semiconductors,mechanical properties,wearable devices
更新于2025-09-10 09:29:36
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Construction of donor-acceptor type conjugated microporous polymers: a fascinating strategy for the development of efficient heterogeneous photocatalysts in organic synthesis
摘要： Metal-free, visible-light driven, solid organic photocatalysts provide a more green and environmentally friendly alternative to traditional metal-based photocatalysts. Donor-Acceepor (D-A) dyads possess a feature of easy to adjust the photoelectric properties, and enhance their photocatalytic performances. Here we report a fascinating strategy for screening excellent organic porous photocatalysts through oxidative coupling of single D-A based monomer, which has still an important advantage to ensure uniformity of polymer structure except for the inherent characteristics of D-A polymers. According to this strategy, three D-A typed conjugated microporous polymer (DA-CMP) photocatalysts consisting of alternating electron-rich (carbazole) and electron-deficient (benzene, 4,7-diphenyl-2,1,3-benzothiadiazole or anthraquinone) units have been synthesized, and their porosity and photoelectric properties including adsorption, emission, lifetime, optical bandgaps, energy levels and transient photocurrent response as well as photocatalytic activity, were conveniently tuned by selecting different D-A monomers with tunable electron-deficient moiety. These DA-CMPs were exploited as metal-free photocatalysts in the oxidative C-H functionalization reactions in the presence of visible-light and molecular oxygen. They showed excellent photocatalytic activity, extensive substrate adaptability and outstanding reusability, due to combining some key features like permanent porosity, outstanding stability and optoelectronic properties. In addition, the reaction mechanism for DA-CMP photocatalyzed C-H functionalization reactions under visible-light irradiation was investigated in detail. Moreover, to prove in depth the benefits of the heterogeneous photocatalysis, a continuous flow procedure has been conducted with an excellent yield.
关键词： flow chemistry,aerobic reaction,conjugated microporous polymers,C-H functionalization,heterogeneous photocatalysis
更新于2025-09-10 09:29:36