Dynamic Control of Full‐Colored Emission and Quenching of Photoresponsive Conjugated Polymers by Photostimuli

A series of photoresponsive and full‐colored fluorescent conjugated copolymers is synthesized by combining phenylene‐ and thienylene‐based main chains with photochromic dithienylethene (DE) side chains. Solutions and cast films of the polymers exhibit various colored fluorescence in visible wavelengths of 400?700 nm corresponding to emissions of the conjugated main chain. The fluorescence is reversibly photoswitched between emission and quenching through DE photoisomerization using external stimuli from ultraviolet and visible light irradiation. The reprecipitation method with ultrasonication enables the polymers to form spherical aggregates with diameters of 20?70 nm in water. After investigating and comparing the optical properties, the resulting nanosphere solutions are assumed to exist in an intermediate state between an isolated state (i.e., in solution) and an aggregated state in cast film. The majority of the nanosphere solutions also exhibit the same photoswitchable fluorescence behavior as those in the solutions and the cast films. The results demonstrate that the visible fluorescence of the conjugated copolymers is reversibly switchable between emission and quenching using the photoisomerizing DE side chain regardless of the fluorescent colors and the polymer chain aggregation.     

Electrochromically and Photochromically Controllable Multifunctional OligoEDOT Derivatives

Multifunctional conjugated co‐oligomers with electrochromic and photochromic properties are synthesized by a cross‐coupling polycondensation reaction between bis(trialkylstannyl)‐3,4‐ethylenedioxythiophene and a phenylene or thienylene derivative bearing a photoresponsive dithienylethene (DE) moiety. The oligomer exhibits a reversible change between the neutral and oxidized states of the main chain upon electrochemical doping and dedoping. Furthermore, the oligomer shows reversible photoisomerization between the open and closed forms of the DE group in the side chain upon irradiation with ultraviolet and visible light. As a consequence, the oligomers possess various electronic structures that show cyclically reversible changes via the electrochemical doping and dedoping, and photoisomerization, producing four types of colored films in an oligomer system. Among the four types of electronic structures, only the dopant‐free oligomer film with the open form of the DE group shows visible fluorescence. To the best of our knowledge, the present conjugated oligomers are the first to exhibit both electrochromic and photochromic functions with cyclical reversibility.     

Poly(dithienylethene‐alt‐1,4‐divinylenephenylene)s: Increasing the Molecular Weights in Diarylethene Photochromic Polymers

Thermally irreversible, photochromic dithienylethene‐alt‐dihexyloxyphenylenevinylene and dithienylethene‐alt‐didodecyloxyphenylenevinylene copolymers have been synthesized via the Horner and Wittig reactions, respectively. Both polymers are photochromic in solution and in the solid state. Electronic spectra show that the materials are highly conjugated in both states and the large π‐delocalization along the main chain when the diarylethene moiety is in the closed form gives a decrease of the ring‐opening quantum yield. The increase in molecular weight relative to other backbone dithienylethene polymers allows the preparation of good quality films without the use of supporting polymer matrices; this is an important achievement for the technological application of these photochromic materials.     

Amphiphilic Poly(p‐phenylene)s for Self‐Organized Porous Blue‐Light‐Emitting Thin Films

Micro‐ and nanostructuring of conjugated polymers are of critical importance in the fabrication of molecular electronic devices as well as photonic and bandgap materials. The present report delineates the single‐step self‐organization of highly ordered structures of functionalized poly(p‐phenylene)s without the aid of either a controlled environment or expensive fabrication methodologies. Microporous films of these polymers, with a honeycomb pattern, were prepared by direct spreading of the dilute polymer solution on various substrates, such as glass, quartz, silicon wafer, indium tin oxide, gold‐coated mica, and water, under ambient conditions. The polymeric film obtained from C₁₂PPPOH comprises highly periodic, defect‐free structures with blue‐light‐emitting properties. It is expected that such microstructured, conjugated polymeric films will have interesting applications in photonic and optoelectronic devices. The ability of the polymer to template the facile micropatterning of nanomaterials gives rise to hybrid films with very good spatial dispersion of the carbon nanotubes.     

Synthesis and Patterning of Luminescent CaCO3–Poly(p‐phenylene) Hybrid Materials and Thin Films

Nature employs specialized macromolecules to produce highly complex structures and understanding the role of these macromolecules allows us to develop novel materials with interesting properties. Herein, we report the role of modified conjugated polymers in the nucleation, growth, and morphology of calcium carbonate (CaCO₃) crystals. In situ incorporation of sulfonated poly(p‐phenylene) (s(PPP)) into a highly oriented calcium carbonate matrix is investigated along with the synthesis and patterning of luminescent CaCO₃–PPP hybrid materials. Functionalized PPP with polar and nonpolar groups are used as additives in the mineralization medium. The polymer (P1) with polar groups give iso‐oriented calcite crystals, whereas PPP with an additional alkyl chain (P2) results in vaterite crystals. The crystallization mechanism can be explained based on self‐assembly and aggregation of polymers in an aqueous environment. Such light‐emitting hybrid composites with tunable optical properties are excellent candidates for optoelectronics and biological applications.     

Photophysical Properties of a Series of Poly(ladder‐type phenylene)s

The photophysical properties, i.e., the fluorescence and phosphorescence of a series of blue light‐emitting poly(ladder‐type phenylene)s have been investigated employing continuous‐wave (cw) and time‐resolved photoluminescence (PL) spectroscopy in solid state and dilute solution. The chemically well‐defined polymers vary from two to five bridged phenyl‐rings per monomer unit bearing aryl‐ or alkyl‐substitution at the bridge‐head carbon atoms. It has been found that the fluorescence energy of the polymers and of the corresponding monomers deviates from a simple 1/N dependence, if the number N of bridged‐phenylene rings is increased beyond a certain limit. Time‐resolved fluorescence spectroscopy on thin films showed that apart from the blue fluorescence of the polymers an additional lower energy emission feature exists, which cannot be assigned to keto‐defects and which seems to be an inherent solid state property of this class of materials. Delayed time‐resolved photoluminescence spectroscopy allowed the detection of phosphorescence energies and lifetimes for all investigated polymers. Photoinduced absorption spectroscopy on thin films showed that the triplet‐triplet absorption red‐shifts with increasing monomer length but reaches a constant value for polymers with N ≥ 4. Amplification of light via amplified spontaneous emission (ASE) from thin film slab waveguide structures could be demonstrated for all ladder‐type polymers but the onset threshold value for ASE varies significantly with the polymer structure.     

Synthesis,Characterization, Two‐Photon Absorption,and Optical Limiting Properties of Ladder‐Type Oligo‐p‐phenylene‐Cored Chromophores

This paper reports on the two‐photon absorption (TPA) and related up‐converted emission properties of a novel series of chromophores containing ladder‐type oligo‐p‐phenylenes with various π‐conjugation lengths. The design and synthesis of these ladder‐type two‐photon chromophores are first discussed. An increase in the π‐conjugated length of the ladder‐type oligo‐p‐phenylene for these chromophores leads to an increase in TPA cross‐section together with an increased fluorescence quantum yield. These chromophores exhibit high fluorescence quantum yields because of the rigid planar structure of the ladder‐type oligomers. The chromophore with an enhanced TPA cross‐section together with an increased fluorescence quantum yield would provide significant benefits for two‐photon excited fluorescence based applications. An improved optical limiting behavior was also demonstrated using the ladder‐type pentaphenylene cored chromophore.     

Efficient Conjugated‐Polymer Optoelectronic Devices Fabricated by Thin‐Film Transfer‐Printing Technique

The fabrication of functional multilayered conjugated‐polymer structures with well‐defined organic‐organic interfaces for optoelectronic‐device applications is constrained by the common solubility of many polymers in most organic solvents. Here, we report a simple, low‐cost, large‐area transfer‐printing technique for the deposition and patterning of conjugated‐polymer thin films. This method utilises a planar poly(dimethylsiloxane) (PDMS) stamp, along with a water‐soluble sacrificial layer, to pick up an organic thin film (～20 nm to 1 µm) from a substrate and subsequently deliver this film to a target substrate. We demonstrate the versatility of this transfer‐printing technique and its applicability to optoelectronic devices by fabricating bilayer structures of poly(9,9‐di‐n‐octylfluorene‐alt‐(1,4‐phenylene‐((4‐sec‐butylphenyl)imino)‐1,4‐phenylene))/poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) (TFB/F8BT) and poly(3‐hexylthiophene)/methanofullerene([6,6]‐phenyl C₆₁ butyric acid methyl ester) (P3HT/PCBM), and incorporating them into light‐emitting diodes (LEDs) and photovoltaic (PV) cells, respectively. For both types of device, bilayer devices fabricated with this transfer‐printing technique show equal, if not superior, performance to either blend devices or bilayer devices fabricated by other techniques. This indicates well‐controlled organic‐organic interfaces achieved by the transfer‐printing technique. Furthermore, this transfer‐printing technique allows us to study the nature of the excited states and the transport of charge carriers across well‐defined organic interfaces, which are of great importance to organic electronics.     

Ambient‐Stable,Annealing‐Free,and Ambipolar Organic Field‐Effect Transistors Based on Solution‐Processable Poly(2,2′‐bis(trifluoromethyl)biphenyl‐alt‐2,5‐divinylthiophene) without Long Alkyl Side Chains

An ambipolar conjugated polymer CF₃‐PBTV, poly(2,2′‐bis(trifluoromethyl)biphenyl‐alt‐2,5‐divinylthiophene), consisting of thienylenevinylene as the donor and trifluoromethyl‐substituted biphenyl as the acceptor has been successfully synthesized. CF₃‐PBTV shows solution‐processability without electrically insulating long alkyl side chains. Grazing incidence X‐ray diffraction results suggest a nearly equal population of flat‐on and end‐on domains in CF₃‐PBTV thin film. The excellent ambipolarity of CF₃‐PBTV is demonstrated by well‐equivalent charge mobilities of 0.065 and 0.078 cm² V^?1 s^?1 for p‐ and n‐channel, respectively. The organic field‐effect transistors (OFET) also shows very high on/off ratio (≈10⁷) which is attributed to the relatively large bandgap and low‐lying highest occupied molecular orbital (HOMO) of CF₃‐PBTV. The OFET performance barely changes after the device is stored in ambient conditions for 90 days. The ambient‐stability is attributed to the enhanced oxidative stability from its low‐lying HOMO and the better moisture resistance from its fluorine contents. The performance of CF₃‐PBTV based OFET is annealing independent. It is noteworthy that the solution‐processable, ambipolar, and thienylenevinylene‐containing conjugated polymer without any long alkyl side chains is reported for the first time. And to the best of our knowledge, it is the first ambient‐stable, annealing‐free OFET with well‐equivalent ambipolarity.     

Systematic Investigation of Side‐Chain Branching Position Effect on Electron Carrier Mobility in Conjugated Polymers

Recently, polymer field‐effect transistors have gone through rapid development. Nevertheless, charge transport mechanism and structure‐property relationship are less understood. Here we use strong electron‐deficient benzodifurandione‐based poly(p‐phenylene vinylene) ( BDPPV ) as polymer backbone and develop six BDPPV ‐based polymers ( BDPPV‐C1 to C6 ) with various side‐chain branching positions to systematically study the side‐chain effect on device performance. All the polymers exhibited ambient‐stable n‐type transporting behaviors with the highest electron mobility of up to 1.40 cm² V^?1 s^?1. The film morphologies and microstructures of all the six polymers were systematically investigated. Our results demonstrate that the interchain π–π stacking distance decreases as moving the branching position away from polymer backbones, and an unprecedentedly close π–π stacking distance down to 3.38 Å is obtained for BDPPV‐C4 to C6 . Nonetheless, closer π–π stacking distance does not always correlate with higher electron mobility. Polymer crystallinity, thin film disorder, and polymer packing conformation, which all influenced by side‐chain branching position, are proved to show significant influence on device performance. Our study not only reveals that π–π stacking distance is not the decisive factor on carrier mobility in conjugated polymers but also demonstrates that side‐chain branching position engineering is a powerful strategy to modulate and balance these factors in conjugated polymers.     

Solution‐Processible Blue‐Light‐Emitting Polymers Based on Alkoxy‐Substituted Poly(spirobifluorene)

Alkoxy‐substituted poly(spirobifluorene)s and their copolymers with a triphenylamine derivative have been synthesized by Ni(0)‐mediated polymerization. The polymers were well soluble in common organic solvents. Pure blue‐light emissions without the long wavelength emission of poly(fluorene)s have been observed in the fluorescence spectra of polymer thin films. The light emitting diodes with a device configuration of ITO/PEDT:PSS(30 nm)/polymer(60 nm)/LiF(1 nm)/Al(100 nm) have been fabricated. The electroluminescence spectra showed the blue emissions without the long wavelength emission as observed in the fluorescence spectra. The relatively poor electroluminescence quantum yield of the homopolymer (0.017% @ 20 mA/cm²) with color coordinates of (0.16, 0.07) has been improved by the introduction of triphenylamine moiety, and the copolymer with triphenylamine derivative exhibited an electroluminescence quantum yield of 0.15 % at 20 mA/cm² with color coordinates of (0.16, 0.08). Moreover, the introduction of polar side chains to the spirobifluorene moiety enhanced the device performance and led to the quantum yields of 0.6 to 0.7 % at 20 mA/cm², although there was some expense of color purities.     

Polymers Containing Highly Polarizable Conjugated Side Chains as High‐Performance All‐Organic Nanodielectric Materials

The discovery of nanodipolar π‐conjugated oligomer‐containing polymers as high performance nanodielectric materials with high permittivity and low dielectric loss over a wide range of frequency (100 Hz–4 MHz) is reported. Terthiophene‐containing methacrylate polymers are synthesized by reversible addition fragmentation transfer (RAFT) polymerization. Both X‐ray and thermal studies indicate the formation of small crystalline domains of terthiophene side chains dispersed in amorphous matrix. The highly polarizable and fast‐responsive nanodipoles from the nanoscale crystalline domains (<2 nm) are believed to dictate the performance. These polymers uniquely satisfy nanodipole architectures conjectured two decades ago to guide the design of high performance nanodielectric materials. This unprecedented approach can be generalized to a variety of π‐conjugated oligomer‐containing polymers for the development of high energy density capacitor materials.     

ε‐Branched Flexible Side Chain Substituted Diketopyrrolopyrrole‐Containing Polymers Designed for High Hole and Electron Mobilities

Based on the integrated consideration and engineering of both conjugated backbones and flexible side chains, solution‐processable polymeric semiconductors consisting of a diketopyrrolopyrrole (DPP) backbone and a finely modulated branching side chain (ε‐branched chain) are reported. The subtle change in the branching point from the backbone alters the π?π stacking and the lamellar distances between polymer backbones, which has a significant influence on the charge‐transport properties and in turn the performances of field‐effect transistors (FETs). In addition to their excellent electron mobilities (up to 2.25 cm² V^?1 s^?1), ultra‐high hole mobilities (up to 12.25 cm² V^?1 s^?1) with an on/off ratio (I_on/I_off) of at least 10⁶ are achieved in the FETs fabricated using the polymers. The developed polymers exhibit extraordinarily high electrical performance with both hole and electron mobilities superior to that of unipolar amorphous silicon.     

Nanoporous Low‐κ Polyimide Films via Poly(amic acid)s with Grafted Poly(ethylene glycol) Side Chains from a Reversible Addition–Fragmentation Chain‐Transfer‐Mediated Process

Thermally‐initiated living radical graft polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA) with ozone‐pretreated poly[N,N′‐(1,4‐phenylene)‐3,3′,4,4′‐benzophenonetetra‐carboxylic amic acid] (PAmA) via a reversible addition–fragmentation chain‐transfer (RAFT)‐mediated process was carried out. The chemical compositions and structures of the copolymers were characterized by nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), X‐ray photoelectron spectroscopy (XPS), and molecular weight measurements. The “living” character of the grafted PEGMA side chains was ascertained in the subsequent extension of the PEGMA side chains. Nanoporous low‐dielectric‐constant (low‐κ) polyimide (PI) films were prepared by thermal imidization of the PAmA graft copolymers under reduced argon pressure, followed by thermal decomposition of the side chains in air. The nanoporous PI films obtained from the RAFT‐mediated graft copolymers had well‐preserved PI backbones, porosity in the range of 5–17 %, and pore size in the range of 30–50 nm. The pores were smaller and the pore‐size distribution more uniform than those of the corresponding nanoporous PI films obtained via graft copolymers from conventional free‐radical processes. Dielectric constants approaching 2 were obtained for the nanoporous PI films prepared from the RAFT‐mediated graft copolymers.     

Synthesis of Highly Fluorescent and Soluble 1,2,4‐Linking Hyperbranched Poly(arylenevinylene) Featuring Intramolecular Energy Funneling

The synthesis and optical properties of a highly soluble (>200 mg mL^?1) and highly fluorescent (Φ_F in film = 0.64) 1,2,4‐linking hyperbranched poly(arylenevinylene) (1,2,4‐hb‐PAV) prepared via Wittig reaction of A ₃ (biphenyl‐tricarbaldehyde) and B₂ (phosphonium salt) monomers is reported. The molecular weight of 1,2,4‐hb‐PAV can be precisely controlled by the amount of the base (NaOCH₃) used in the polymerization. The absorption and photoluminescence (PL) spectra of 1,2,4‐hb‐PAV shows distinct red‐shifts compared to conventional 1,3,5‐linking hyperbranched poly(arylenevinylene) (1,3,5‐hb‐PAV), attributed to the extended π‐conjugation along ortho‐ (1,2‐) and para‐ (1,4‐) links. The inherent energy gradient from the shorter branches to the longer conjugated stem in 1,2,4‐hb‐PAV enabled a characteristic energy funneling effect, which is absent in conventional hyperbranched polymer of 1,3,5‐hb‐PAV.     

Intercalating Dye Harnessed Cationic Conjugated Polymer for Real‐Time Naked‐Eye Recognition of Double‐Stranded DNA in Serum

Thiazole orange (TO), an intercalating dye, is integrated into cationic poly(fluorene‐alt‐phenylene) (PFP) to develop a macromolecular multicolor probe (PFPTO) for double‐stranded DNA (dsDNA) detection. This polymer design not only takes advantage of the high affinity between TO and dsDNA to realize dsDNA recognition in biological media, but also brings into play the light‐harvesting feature of conjugated polymers to amplify the signal output of TO in situ. PFPTO differentiates dsDNA from single‐stranded DNA (ssDNA) more effectively upon excitation of the conjugated backbone relative to that upon direct excitation of TO as a result of efficient fluorescence resonance energy transfer from the polymer backbone to the intercalated TO. In the presence of dsDNA, energy transfer within PFPTO is more efficient as compared to that for free TO/PFP system, which leads to better dsDNA discriminability for PFPTO in contrast to that for TO/PFP. The distinguishable fluorescent color for PFPTO solutions in the presence of dsDNA allows naked‐eye detection of dsDNA with the assistance of a hand‐held UV lamp. The significant advantage of this macromolecular fluorescent probe is that naked‐eye detection of label‐free dsDNA can be performed in biological media in real‐time.     

Conjugated Polyelectrolytes as Light‐Up Macromolecular Probes for Heparin Sensing

Two cationic poly(fluorene‐alt‐benzothiadiazole)s with different side chains are designed and synthesized. Both polymers show low fluorescence in aqueous solution due to the charge‐transfer character of the polymer's excited states. Fluorescence turn‐on biosensors for heparin detection and quantification are developed, taking advantage of complexation‐induced aggregation, which increases the polymer fluorescence in aqueous solution. It is found that good polymer water‐solubility is beneficial to the sensitivity and fluorescence contrast of the heparin turn‐on sensor as a result of the low fluorescence background. Moreover, stronger complexation between the polymer/heparin leads to a substantially larger fluorescence increase in the presence of heparin relative to that in the presence of its analog, hyaluronic acid (HA), allowing discrimination of heparin from HA. Heparin quantification with a practical calibration range covering the whole therapeutic dosing levels (0.2–8 U mL⁻¹) is realized based on the polymer with good water‐solubility. This investigation provides a new insight for designing conjugated polymers with a light‐up signature for biomolecular sensing.     

Origin of the Reduced Fill Factor and Photocurrent in MDMO‐PPV:PCNEPV All‐Polymer Solar Cells

The photogeneration mechanism in blends of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene vinylene] (MDMO‐PPV) and poly[oxa‐1,4‐phenylene‐(1‐cyano‐1,2‐vinylene)‐(2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylene)‐1,2‐(2‐cyanovinylene)‐1,4‐phenylene] (PCNEPV) is investigated. The photocurrent in the MDMO‐PPV:PCNEPV blends is strongly dependent on the applied voltage as a result of a low dissociation efficiency of the bound electron–hole pairs. The dissociation efficiency is limited by low carrier mobilities, low dielectric constant, and the strong intermixing of the polymers, leading to a low fill factor and a reduced photocurrent at operating conditions. Additionally, electrons trapped in the PCNEPV phase recombine with the mobile holes in the MDMO‐PPV phase at the interface between the two polymers, thereby affecting the open‐circuit voltage and increasing the recombination losses. At an intensity of one sun, Langevin recombination of mobile carriers dominates over trap‐assisted recombination.     

Surface‐Directed Phase Separation of Conjugated Polymer Blends for Efficient Light‐Emitting Diodes

The ability to control organic‐organic interfaces in conjugated polymer blends is critical for further device improvement. Here, we control the phase separation in blends of poly(9,9‐di‐n‐octylfluorene‐alt‐benzothiadiazole) (F8BT) and poly(9,9‐di‐n‐octylfluorene‐alt‐(1,4‐phenylene‐((4‐sec‐butylphenyl)imino)‐1,4‐phenylene) (TFB) via chemical modification of the substrate by microcontact printing of octenyltrichlorosilane molecules. The lateral phase‐separated structures in the blend film closely replicate the underlying micrometer‐scale chemical pattern. We found nanometer‐scale vertical segregation of the polymers within both lateral domains, with regions closer to the substrate being substantially pure phases of either polymer. Such phase separation has important implications for the performance of light‐emitting diodes fabricated using these patterned blend films. In the absence of a continuous TFB wetting layer at the substrate interface, as typically formed in spin‐coated blend films, charge carrier injection is confined in the well‐defined TFB‐rich domains. This confinement leads to high electroluminescence efficiency, whereas the overall reduction in the roughness of the patterned blend film results in slower decay of device efficiency at high voltages. In addition, the amount of surface out‐coupling of light in the forward direction observed in these blend devices is found to be strongly correlated to the distribution of periodicity of the phase‐separated structures in the active layer.