Toward the Prediction and Control of Glass Transition Temperature for Donor–Acceptor Polymers

Semiconducting donor–acceptor (D–A) polymers have attracted considerable attention toward the application of organic electronic and optoelectronic devices. However, a rational design rule for making semiconducting polymers with desired thermal and mechanical properties is currently lacking, which greatly limits the development of new polymers for advanced applications. Here, polydiketopyrrolopyrrole (PDPP)‐based D–A polymers with varied alkyl side‐chain lengths and backbone moieties are systematically designed, followed by investigating their thermal and thin film mechanical responses. The experimental results show a reduction in both elastic modulus and glass transition temperature (T_g) with increasing side‐chain length, which is further verified through coarse‐grained molecular dynamics simulations. Informed from experimental results, a mass‐per‐flexible bond model is developed to capture such observation through a linear correlation between T_g and polymer chain flexibility. Using this model, a wide range of backbone T_g over 80 °C and elastic modulus over 400 MPa can be predicted for PDPP‐based polymers. This study highlights the important role of side‐chain structure in influencing the thermomechanical performance of conjugated polymers, and provides an effective strategy to design and predict T_g and elastic modulus of future new D–A polymers.     

Designing a Length-Modulated Azide Photocrosslinker to Improve the Stretchability of Semiconducting Polymers

To impart high stretchability to semiconducting polymers, researchers have used a photocrosslinking approach based on the nitrene chemistry of an azide-incorporated molecular additive. However, understanding of the molecular design of azide crosslinkers with respect to their effects on the electrical and mechanical properties of semiconducting polymer thin films is lacking. In this study, the effects of an azide photocrosslinker's molecular length and structure on the microstructural, electrical features, and stretchability of photocrosslinked conjugated polymer films is investigated. For a systematic comparison, a series of nitrene-induced photocrosslinkers (n-NIPSs) with different numbers of ethylene glycol repeating units (n = 1, 4, 8, 13) that bridge two tetrafluoro-aryl azide end groups is synthesized. Two semicrystalline conjugated polymers and two nearly amorphous conjugated polymers are co-processed with n-NIPSs and crosslinked by brief exposure to UV light. It is found that, among the synthesized n-NIPSs, the shortest one (1-NIPS) is the most efficient in improving the stretchability of crosslinked indacenodithiophene-benzothiadiazole films and that the improvement is achieved only with nearly amorphous polymers, not with semicrystalline conjugated polymers. On the basis of systematic studies, it is suggested that crosslinking density in amorphous regions is important in improving thin film stretchability.     

Acylhydrazones as Reversible Covalent Crosslinkers for Self‐Healing Polymers

The utilization of dynamic covalent and noncovalent bonds in polymeric materials offers the possibility to regenerate mechanical damage, inflicted on the material, and is therefore of great interest in the field of self‐healing materials. For the design of a new class of self‐healing materials, methacrylate containing copolymers with acylhydrazones as reversible covalent crosslinkers are utilized. The self‐healing polymer networks are obtained by a bulk polymerization of an acylhydrazone crosslinker and commercially available methacrylates as comonomers to fine‐tune the T_g of the systems. The influence of the amount of acylhydrazone crosslinker and the self‐healing behavior of the polymers is studied in detail. Furthermore, the basic healing mechanism and the corresponding mechanical properties are analyzed.     

Strong,Tailored, Biocompatible Shape‐Memory Polymer Networks

Shape‐memory polymers are a class of smart materials that have recently been used in intelligent biomedical devices and industrial applications for their ability to change shape under a predetermined stimulus. In this study, photopolymerized thermoset shape‐memory networks with tailored thermomechanics are evaluated to link polymer structure to recovery behavior. Methyl methacrylate (MMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) are copolymerized to create networks with independently adjusted glass transition temperatures (T_g) and rubbery modulus values ranging from 56 to 92 °C and 9.3 to 23.0 MPa, respectively. Free‐strain recovery under isothermal and transient temperature conditions is highly influenced by the T_g of the networks, while the rubbery moduli of the networks has a negligible effect on this response. The magnitude of stress generation of fixed‐strain recovery correlates with network rubbery moduli, while fixed‐strain recovery under isothermal conditions shows a complex evolution for varying T_g. The results are intended to help aid in future shape‐memory device design and the MMA‐co‐PEGDMA network is presented as a possible high strength shape‐memory biomaterial.     

Electrochemically Nanostructured Polyvinylferrocene/Polypyrrole Hybrids with Synergy for Energy Storage

Unconjugated redox polymers, such as polyvinylferrocene (PVF), have rarely been used for energy storage due to their low intrinsic conductivity. Conducting polymers with conjugated backbones, though conductive, may suffer from insufficient exposure to the electrolyte due to the often formed nonporous structures. The present work overcomes this limitation via simultaneous electropolymerization of pyrrole and electroprecipitation of PVF on electrode surfaces. This synthesis method relies on the π–π stacking interactions between the aromatic pyrrole monomers and the metallocene moieties of PVF. This fabrication process results in a highly porous polymer film, which enhances the ion accessibility to polypyrrole (PPy). PPy serves as a “molecular wire,” improving the electronic conductivity of the hybrid and the utilization efficiency of ferrocene. The PVF/PPy hybrid exhibited a specific capacitance of 514.1 F g^?1 _, which significantly exceeds those of PPy (27.3 F g^?1) and PVF (79.0 F g^?1), respectively. This approach offers an alternative to nanocarbon materials for improving the electronic conductivity of polymer hybrids, and suggests a new strategy for fabricating nanostructured polymer hybrids. This strategy can potentially be applied to various polymers with π‐conjugated backbones and redox polymers with metallocene moieties for applications such as energy storage, sensing, and catalysis.     

Impedance Measurements as a Simple Tool to Control the Quality of Conjugated Polymers Designed for Photovoltaic Applications

The problem of batch‐to‐batch variation of electronic properties and purity of conjugated polymers used as electron donor and photon harvesting materials in organic solar cells is addressed. A simple method is developed for rapid analysis of electronic quality of polymer‐based materials. It is shown that appearance of impurities capable of charge trapping changes electrophysical properties of conjugated polymers. In particular, a clear correlation between the effective relaxation time τeff and relative photovoltaic performance (η/η_max) is revealed for samples of poly(3‐hexylthiophene) intentionally polluted with a palladium catalyst. This dependence is also valid for all other investigated samples of conjugated polymers. Therefore, fast impedance measurements at three different frequencies allow one to draw conclusions about the purity of the analyzed polymer sample and even estimate its photovoltaic performance. The developed method might find extensive applications as a simple tool for product quality control in the laboratory and industrial‐scale production of conjugated polymers for electronic applications.     

High‐Strain Shape‐Memory Polymers

Shape‐memory polymers (SMPs) are self‐adjusting, smart materials in which shape changes can be accurately controlled at specific, tailored temperatures. In this study, the glass transition temperature (T_g) is adjusted between 28 and 55 °C through synthesis of copolymers of methyl acrylate (MA), methyl methacrylate (MMA), and isobornyl acrylate (IBoA). Acrylate compositions with both crosslinker densities and photoinitiator concentrations optimized at fractions of a mole percent demonstrate fully recoverable strains at 807% for a T_g of 28 °C, at 663% for a T_g of 37 °C, and at 553% for a T_g of 55 °C. A new compound, 4,4′‐di(acryloyloxy)benzil (referred to hereafter as Xini) in which both polymerizable and initiating functionalities are incorporated in the same molecule, was synthesized and polymerized into acrylate shape‐memory polymers, which were thermomechanically characterized yielding fully recoverable strains above 500%. The materials synthesized in this work were compared to an industry standard thermoplastic SMP, Mitsubishi's MM5510, which showed failure strains of similar magnitude, but without full shape recovery: residual strain after a single shape‐memory cycle caused large‐scale disfiguration. The materials in this study are intended to enable future applications where both recoverable high‐strain capacity and the ability to accurately and independently position T_g are required.     

Solution-Processable and Thermostable Super-Strong Poly(aryl ether ketone) Supramolecular Thermosets Cross-Linked with Dynamic Boroxines

High-performance engineering polymers (HPEPs) are mechanically robust but difficult to be processed and recycled. Aiming to solve such a problem, herein, supramolecular thermosets with high mechanical strength comparable to HPEPs are fabricated by dynamically cross-linking low-molecular-weight poly(aryl ether ketone)s (PAEKs) with boroxines (denoted as PAEK-B₃O₃). The PAEK-B₃O₃ supramolecular thermosets are solution-processable, thermally stable, and recyclable. By tailoring the molecular weight (M_n) of PAEK, the PAEK-B₃O₃ thermosets can exhibit a tensile strength from ≈60.5 to ≈97.8 MPa and Young's modulus from ≈1.59 to ≈4.10 GPa. The mechanically strongest PAEK-B₃O₃ thermosets, which are derived from PAEK with an M_n of ≈9400, have a tensile strength of ≈97.8 MPa, Young's modulus of ≈1.93 GPa, and glass transition temperature (T_g) of ≈154.0 °C. Such PAEK-B₃O₃ thermosets retain a substantial amount of boroxine cross-linkers when the temperature is close to T_g, which guarantees their high mechanical strength at high temperatures. The PAEK-B₃O₃ thermosets can be solution-processed to products of different shapes and further strengthened by the introduction of polyhedral oligomeric silsesquioxanes modified with phenylboronic acids. Due to the high reversibility of boroxines, the PAEK-B₃O₃ thermosets can be conveniently re-processed and recycled in the presence of dioxane/ethanol mixture solvent to regain their original mechanical strength.     

Exploiting Microphase‐Separated Morphologies of Side‐Chain Liquid Crystalline Polymer Networks for Triple Shape Memory Properties

We report a new strategy to achieve triple shape memory properties by using side‐chain liquid crystalline (SCLC) type random terpolymer networks (XL‐ TP‐n), where n is the length of flexible methylene spacer (n = 5, 10, and 15) to link backbone and mesogen. A lower glass transition temperature (T_g = T_low) and a higher liquid crystalline clearing temperature (T_cl = T_high) of XL‐TP‐n serve as molecular switches to trigger a shape memory effect (SME). Two different triple shape creation procedures (TSCPs), thermomechanical treatments to obtain temporary shapes prior to the proceeding recovery step, are used to investigate the triple shape memory behavior of XL‐TP‐n. The discrete T_g and T_cl as well as unique microphase‐separated morphologies (backbone‐rich and mesogen‐rich domains) within smectic layers of XL‐TP‐n enables triple shape memory properties. Motional decoupling between backbone‐rich and mesogen‐rich domains is also critical to determine the resulting macroscopic shape memory properties. Our strategy for obtaining triple shape memory properties will pave the way for exploiting a broad range of SCLC polymers to develop a new class of actively moving polymers.     

Shape‐Memory Microfluidics

Materials with embedded vascular networks afford rapid and enhanced control over bulk material properties including thermoregulation and distribution of active compounds such as healing agents or stimuli. Vascularized materials have a wide range of potential applications in self‐healing systems and tissue engineering constructs. Here, the application of vascularized materials for accelerated phase transitions in stimuli‐responsive microfluidic networks is reported. Poly(ester amide) elastomers are hygroscopic and exhibit thermo‐mechanical properties (T_g ≈ 37 °C) that enable heating or hydration to be used as stimuli to induce glassy‐rubbery transitions. Hydration‐dependent elasticity serves as the basis for stimuli‐responsive shape‐memory microfluidic networks. Recovery kinetics in shape‐memory microfluidics are measured under several operating modes. Perfusion‐assisted delivery of stimulus to the bulk volume of shape‐memory microfluidics dramatically accelerates shape recovery kinetics compared to devices that are not perfused. The recovery times are 4.2 ± 0.1 h and 8.0 ± 0.3 h in the perfused and non‐perfused cases, respectively. The recovery kinetics of the shape‐memory microfluidic devices operating in various modes of stimuli delivery can be accurately predicted through finite element simulations. This work demonstrates the utility of vascularized materials as a strategy to reduce the characteristic length scale for diffusion, thereby accelerating the actuation of stimuli‐responsive bulk materials.     

Molecularly Engineered Biodegradable Polymer Networks with a Wide Range of Stiffness for Bone and Peripheral Nerve Regeneration

To satisfy different mechanical requirements in hard and soft tissue replacements, a series of biodegradable and crosslinkable copolymers of poly(propylene fumarate)‐co‐polycaprolactone (PPF‐co‐PCL) are synthesized and employed to fabricate 2D disks and 3D scaffolds via photocrosslinking. Thermal properties such as the glass transition temperature (T_g) and melting temperature (T_m) of the PPF‐co‐PCL networks can be controlled efficiently by varying the PCL composition (φ_PCL). As a result, their mechanical properties vary significantly from hard and stiff materials to soft and flexible ones with increasing φ_PCL, making them attractive candidate materials for bone and peripheral nerve regeneration, respectively. Several PPF‐co‐PCL formulations are selected to perform in vitro cell studies using mouse pre‐osteoblastic MC3T3‐E1, rat Schwann cell precursor line (SPL201), and pheochromocytoma (PC12) cells, and in vivo animal testing in the rat femur bone defect model and in the rat sciatic nerve transection model. The formation of new bone in the porous bone scaffolds with a low φ_PCL and guided axon growth through the nerve conduits with a higher φ_PCL suggest that crosslinked PPF‐co‐PCLs have appropriate compatibility and functionality. Furthermore, the role of surface stiffness in modulating cellular behavior and functions is verified on the crosslinked PPF‐co‐PCL surfaces without any pretreatments.     

Idealized geometric and chemical models for conjugated conducting polymer systems

Idealized geometric and chemical models based on ordered molecular systems are used to discuss the structural, optical, and charge-transfer properties of conjugated polymers such as polyacetylene, (CH)_x, and poly-p-phenylene, (C₆ H₄ )_x. . Specific interchain interactions are proposed to contribute to the optical properties of (CH)_x and possible experimental manifestations are discussed. The interaction of MX₅ moi-eties with conjugated polymers are discussed in terms of com-peting processes involving covalent bond-breaking and-forma-tion vs. electron transfer. The possible stabilization_by the polymers of presently unknown species, such as AsF₅ , is discussed. A geometric origin is proposed for the con-ductivity anisotropy of (CH)_x and this approach is used to speculate on a possible new type of two-dimensional conductor.     

Fully Printed Organic Electrochemical Transistors from Green Solvents

To achieve the full potential of scalable and cost‐effective organic electronic devices, developments are being made in both academic and industry environments to move toward continuous solution‐processing techniques that make use of safe and environmentally benign “green” solvents. In this work, the first example of a transistor device that is fully solution processed using only green solvents is demonstrated. This achievement is enabled through a novel multistage cleavable side chain process that provides aqueous solubility for semiconducting conjugated polymers, paired with aqueous inkjet printing of PEDOT:PSS electrodes, and a solution deposited ion gel electrolyte as the dielectric layer. The resulting organic electrochemical transistor devices operate in accumulation mode and reach maximum transconductance values of 1.1 mS at a gate voltage of ? 1 V. Normalizing the transconductance value to the channel dimensions yields g_m/W = 2200 S m^?1 (µC* = 22 F cm^?1 V^?1 s^?1), making these devices suitable for a range of applications requiring small signal amplification such as transistors, biosensors, and ion pumps. This new material design and device process paves the way toward scalable, safe, and efficient production of organic electronic devices.     

Layer‐Structured Photoconducting Polymers: A New Class of Photorefractive Materials

We study the photorefractive (PR) properties of a new kind of low glass‐transition temperature (T_g) polymer composite based on layered photoconductive polymers, poly(p‐phenylene terephthalate) carbazoles (PPT‐CZs). These photoconductors consist of the rigid backbone of PPT with pendant oxyalkyl CZ groups. The compounds are doped with the photosensitizer C₆₀ and nonlinear optical chromophores diethylaminodicyanostyrene (DDCST), and no plasticizers are added. When the host polymers are mixed with various PR ingredients, the layers are preserved and their layer distance increases, indicating that all the guest molecules are confined to the nanoscale interlayer space. These composites showed very low T_g values (< ? °C). Despite the absence of a plasticizer and the lower concentration of the carbazole photoconductive moieties as compared to poly(N‐vinylcarbazole) systems, these materials show excellent PR properties, i.e., a PR gain of Γ = 250 cm^–1 under an external electric field of 60 V μm^–1, and diffraction efficiency and PR sensitivity of 93 % and 24 ± 7 cm² kJ^–1 at E = 100 V μm^–1, respectively.     

Modulating Backbone Conjugation of Polymeric Thermally Activated Delayed Fluorescence Emitters for High-Efficiency Blue OLEDs

Blue conjugated polymers-based OLEDs with both high efficiency and low efficiency roll-off are under big challenge. Herein, a strategy of local conjugation is proposed to construct high-efficiency blue-emitting conjugated polymers, in which the conjugation degree of polymeric backbones is adjusted by inserting different spacers. In this way, the energy level of triplet state and the energy transfer direction of the polymeric main-chains can be effectively regulated. Benefiting from such fine regulation, the prepared alternative copolymers Alt-PB36 with local conjugated main-chains can better suppress the accumulation of long-lived triplet excitons comparing with the complete conjugated polymers. The higher PLQY of Alt-PB36 also verifies the effective energy transfer from the polymeric main-chains to the TADF units. Accordingly, Alt-PB36 based solution-processed OLEDs achieve an EQE_max of 11.6% and a very low efficiency roll-off of 2.8% at 100 cd m⁻² and 15.2% at 500 cd m⁻². This result represents the best efficiency among blue light-emitting conjugated polymer-based OLEDs so far under high luminance.     

Influence of the Electron Deficient Co‐Monomer on the Optoelectronic Properties and Photovoltaic Performance of Dithienogermole‐based Co‐Polymers

A series of donor–acceptor (D–A) conjugated polymers utilizing 4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophene ( DTG ) as the electron rich unit and three electron withdrawing units of varying strength, namely 2‐octyl‐2H‐benzo[d][1,2,3]triazole ( BTz ), 5,6‐difluorobenzo[c][1,2,5]thiadiazole ( DFBT ) and [1,2,5]thiadiazolo[3,4‐c]pyridine ( PT ) are reported. It is demonstrated how the choice of the acceptor unit ( BTz , DFBT , PT ) influences the relative positions of the energy levels, the intramolecular transition energy (ICT), the optical band gap (E_g^opt), and the structural conformation of the DTG ‐based co‐polymers. Moreover, the photovoltaic performance of poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐([1,2,5]thiadiazolo[3,4‐c]pyridine)] ( PDTG‐PT ), poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐(2‐octyl‐2H‐benzo[d][1,2,3]triazole)] ( PDTG‐BTz ), and poly[(4,4‐bis(2‐ethylhexyl)‐4H‐germolo[3,2‐b:4,5‐b′]dithiophen‐2‐yl)‐(5,6‐difluorobenzo[c][1,2,5]thiadiazole)] ( PDTG‐DFBT ) is studied in blends with [6,6]‐phenyl‐C₇₀‐butyric acid methyl ester ( PC₇₀BM ). The highest power conversion efficiency (PCE) is obtained by PDTG‐PT (5.2%) in normal architecture. The PCE of PDTG‐PT is further improved to 6.6% when the device architecture is modified from normal to inverted. Therefore, PDTG‐PT is an ideal candidate for application in tandem solar cells configuration due to its high efficiency at very low band gaps (E_g^opt = 1.32 eV). Finally, the 6.6% PCE is the highest reported for all the co‐polymers containing bridged bithiophenes with 5‐member fused rings in the central core and possessing an E_g^opt below 1.4 eV.     

Fabrication of Reversibly Crosslinkable, 3‐Dimensionally Conformal Polymeric Microstructures

Multifaceted porous materials were prepared through careful design of star polymer functionality and properties. Functionalized core crosslinked star (CCS) polymers with a low glass transition temperature (T_g) based on poly(methyl acrylate) were prepared having a multitude of hydroxyl groups at the chain ends. Modification of these chain ends with 9‐anthracene carbonyl chloride introduces the ability to reversibly photocrosslink these systems after the star polymers were self‐assembled by the breath figure technique to create porous, micro‐structured films. The properties of the low T_g CCS polymer allow for the formation of porous films on non‐planar substrates without cracking and photo‐crosslinking allows the creation of stabilized honeycomb films while also permitting a secondary level of patterning on the film, using photo‐lithographic techniques. These multifaceted porous polymer films represent a new generation of well‐defined, 3D microstructures.     

Substantial Cyano‐Substituted Fully sp2‐Carbon‐Linked Framework: Metal‐Free Approach and Visible‐Light‐Driven Hydrogen Evolution

Polymeric semiconductors are emerging as a kind of competitive photocatalysts for hydrogen evolution due to their well‐tunable structures, versatile functionalization, and low‐cost processibility. In this work, a series of conjugated porous polymers with substantial cyano‐substituted fully sp²‐carbon frameworks are efficiently synthesized by using electron‐deficient tricyanomesitylene as a key building block to promote an organic base‐catalyzed Knoevenagel condensation with various aldehyde‐substituted arenes. The resulting porous polymers feature donor‐acceptor structures with π‐extended conjugation, rendering them with distinct semiconducting properties. They possess hierarchically porous structures, nanoscale morphologies, and intriguing wettability. These promising physical characters, finely tailorable by varying the arene units, are essentially relevant to the abundant cynao substituents over the whole frameworks. The as‐prepared porous polymers exhibit excellent visible‐light‐driven photocatalytic activity for water‐splitting hydrogen evolution with apparent quantum yield up to 2.0% at 420 nm or 1.9% at 470 nm, among the highest values yet reported for porous polymer‐based photocatalysts, also representing the first example of such kinds of catalysts formed through a metal‐free‐catalyzed carbon–carbon coupling reaction.     

The Energy of Charge‐Transfer States in Electron Donor–Acceptor Blends: Insight into the Energy Losses in Organic Solar Cells

Here, a general experimental method to determine the energy E_CT of intermolecular charge‐transfer (CT) states in electron donor–acceptor (D–A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D–A blends to correct for a constant Coulombic term. It is shown that E_CT correlates linearly with the open‐circuit voltage (V_oc) of photovoltaic devices in D–A blends via eV_oc = E_CT ? 0.5 eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S₁ with energy E_g) in the blend to the CT state (S₁ → CT) occurs when E_g ? E_CT > 0.1 eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (E_T) of D or A (CT → T₁) can occur when E_CT ? E_T > 0.1 eV. From these relations, it is concluded that in D–A blends optimized for photovoltaic action: i) the maximum attainable V_oc is ultimately set by the optical band gap (eV_oc = E_g ? 0.6 eV) and ii) the singlet–triplet energy gap should be ΔE_ST < 0.2 eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area.     

High‐Performance Ambipolar Polymers Based on Electron‐Withdrawing Group Substituted Bay‐Annulated Indigo

For donor–acceptor conjugated polymers, it is an effective strategy to improve their electron mobilities by introducing electron‐withdrawing groups (EWGs, such as F, Cl, or CF₃) into the polymer backbone. However, the introduction of different EWGs always requires a different synthetic approach, leading to additional arduous work. Here, an effective two‐step method is developed to obtain EWG substituted bay‐annulated indigo (BAI) units. This method is effective to introduce various EWGs (F, Cl, or CF₃) into BAI at different substituted positions. Based on this method, EWG substituted BAI acceptors, including 2FBAI, 2ClBAI, and 2CF₃BAI, are reported for the first time. Furthermore, four polymers of PBAI‐V, P2FBAI‐V, P2ClBAI‐V, and P4OBAI‐V are developed. All the polymers show ambipolar transport properties. Particularly, P2ClBAI‐V exhibits remarkable hole and electron mobilities of 4.04 and 1.46 cm² V^?1 s^?1, respectively. These mobilities are among the highest values for BAI‐based polymers.