Helically π‐Stacked Conjugated Polymers Bearing Photoresponsive and Chiral Moieties in Side Chains: Reversible Photoisomerization‐Enforced Switching Between Emission and Quenching of Circularly Polarized Fluorescence

Novel multifunctional conjugated polymers, [poly(p‐phenylene)s and poly(bithienylene‐phenylene)s with (R)‐ and (S)‐configurations], which have fluorescence, chirality, and photoresponsive properties, have been designed and synthesized. The polymers are composed of π‐conjugated main chains, where poly(p‐phenylene) and poly(bithienylene‐phenylene) are fluorescence moieties, and the side chains of the photochromic dithienylethene moiety are linked with chiral alkyl groups. The polymer films exhibit right‐ or left‐handed circularly polarized fluorescence (CPF) and also show reversible quenching and emitting behaviors as a result of photochemical isomerization of the dithienylethene moiety upon irradiation with ultraviolet and visible light. This is the first report realizing the reversible switching of CPF using chirality and photoresponsive properties.     

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.     

Synthesis of Novel Photochromic Films by Oxidation Polymerization of Diarylethenes Containing Phenol Groups

We report the synthesis of some diarylethene derivatives attached to phenol moieties, which show remarkable photochromic reactions. A dithienylethene group attached to the o‐phenol moiety (1,2‐bis[2,4‐dimethyl‐5‐(o‐hydroxyphenyl)‐3‐thienyl]hexafluorocyclopentene) was polymerized according to Hay's method; the resulting film was insoluble to any solvents, and showed no absorption band attributable OH group in its IR spectrum. Isomeric dithienylethenes attached to m‐ and p‐phenol moieties did not form films under the same oxidation conditions, but instead formed films by copolymerization with 4,4′‐dihydroxyphenyl ether. Although the homopolymer film and copolymer films showed reversible photochromic reactions by alternate irradiation with UV and visible light, the coloration was not remarkable. Polymerization of closed‐ring isomers of the dithienylethenes did not give pre‐polymers and instead decomposed, while the closed‐ring isomer of a bisbenzothienylethene derivative attached to the o‐phenol moiety (1,2‐bis[2‐methyl‐6‐(o‐hydroxyphenyl)‐1‐benzothiophen‐3‐yl]hexafluorocyclopentene) formed a polymer film by the same procedure. This polymer film showed a remarkable photochromic reaction, indicating the photo‐reactive conformation was fixed in polymer matrix, and X‐ray diffraction measurements show that the film is in the amorphous phase. The photochromic reaction can also be monitored by IR spectroscopy, making it applicable for non‐destructive read‐out recording films.     

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.     

Optimizing Light‐Harvesting Polymers via Side Chain Engineering

A series of conjugated polymers using naphtho[1,2‐c:5,6‐c]bis[1,2,5]thiadiazole and benzodithiophene alternating backbone is synthesized to investigate the effect of side chain substitution on conjugated donor–acceptor polymer on electronic, morphological, and photovoltaic properties. It is found that light absorption and frontier energy levels of the resultant polymers are strongly affected by the side chains. The thin film morphology, crystal structure, crystallinity, and orientation also depend on the side chains; the side chain type affects more in the π–π stacking direction, while the side chain density plays a significant role in the lamellar packing direction. The thickness of the active layer also influences the performance of the solar cells with some materials showing enhanced performance with thicker active layers. The best solar cell device in this study has power conversion efficiencies of 8.14%, among the highest in materials of similar structure.     

Copper‐Free Clickable Coatings

The copper‐catalyzed azide–alkyne 1,3‐dipolar cycloaddition (CuAAC) is extensively used for the functionalization of well‐defined polymeric materials. However, the necessity for copper, which is inherently toxic, limits the potential applications of these materials in the area of biology and biomedicine. Therefore, the first entirely copper‐free procedure for the synthesis of clickable coatings for the immobilization of functional molecules is reported. In the first step, azide‐functional coatings are prepared by thermal crosslinking of side‐chain azide‐functional polymers and dialkyne linkers. In a second step, three copper‐free click reactions (i.e., the Staudinger ligation, the dibenzocyclooctyne‐based strain‐promoted azide–alkyne [3+2] cycloaddition, and the methyl‐oxanorbornadiene‐based tandem cycloaddition?retro‐Diels?Alder (crDA) reaction) are used to functionalize the azide‐containing surfaces with fluorescent probes, allowing qualitative comparison with the traditional CuAAC.     

Room Temperature Fluorescent Conjugated Polymer Gums

High molecular weight poly(diphenylacetylene) [PDPA] derivatives are introduced as fluorescent, soft conjugated polymers that exist in the gum state at room temperature. The gum‐like behavior of the polymers is easily modified according to the side alkyl chain length and substitution position. Long alkyl chain‐coupled PDPA derivatives provide soft and sticky gums at room temperature. Manual kneading of gum polymers produce soft films with very smooth surfaces. The gum polymers show an endothermic transition due to the melting of long alkyl chains. The X‐ray diffraction of gum polymers reveals a new signal due to the molten aliphatic chains. The gum polymers show significant viscoelastic relaxation at the melting temperature of the alkyl side chains. The dynamic thermo‐mechanical analysis (DTMA) of gum polymers at room temperature suggest that the meta‐substituted polymer is softer and stickier than para‐polymer. Rheological analysis suggests that the meta‐polymer has less entanglement than para‐polymer. The fluorescence emission of gum polymer is quite intense in the film and solution. The gum polymer film is readily stretched to produce a uniaxually oriented film. Stretching and subsequent relaxation of elastomer‐supported gum polymer film generate buckles perpendicular to the axis of strain. The gum polymer film accommodates the large strain without cracking and delamination.     

Biodegradable Supramolecular Materials Based on Cationic Polyaspartamides and Pillar[5]arene for Targeting Gram‐Positive Bacteria and Mitigating Antimicrobial Resistance

The increasing number of infections caused by pathogenic bacteria has severely affected human society, for instance, numerous deaths are from Gram‐positive methicillin‐resistant Staphylococcus aureus (MRSA) each year. In this work, four biodegradable antibacterial polymer materials based on cationic polyaspartamide derivatives with different lengths of side chains are synthesized through the ring‐opening polymerization of β‐benzyl‐l ‐aspartate N‐carboxy anhydride, followed by an aminolysis reaction and subsequent methylation reaction. The cationic quaternary ammonium groups contribute to the insertion of the catiomers into the negatively charged bacterial membranes, which leads to membranolysis, the leakage of bacterial content, and the death of pathogens. Except for wiping out MRSA readily, the biodegradable polymers possessing alterable antibacterial potency can minimize the possibility of microbial resistance and mitigate drug accumulation by virtue of their cleavable backbone. To manipulate the poor biocompatibility of these polycations, carboxylatopillar[5]arene (CP[5]A) is introduced to the polymeric antibacterial catiomers through the supramolecular host–guest approach to obtain novel antibacterial materials with pH‐sensitive characteristics (with CP[5]A departure from cationic quaternary ammonium compounds under acid conditions) and selective targeting of Gram‐positive bacteria. Finally, the facile and robust antibacterial system is successfully applied to in vivo MRSA‐infected wound healing, providing a significant reference for the construction of advanced antibacterial biomaterials.     

Unconjugated Side‐Chain Engineering Enables Small Molecular Acceptors for Highly Efficient Non‐Fullerene Organic Solar Cells: Insights into the Fine‐Tuning of Acceptor Properties and Micromorphology

2D conjugated side‐chain engineering is an effective strategy that is widely utilized to construct benzodithiophene‐based polymers. Herein, an unconjugated side‐chain strategy to design fused‐benzodithiophene‐based non‐fullerene small molecule acceptors (SMAs) via vertical aromatic side‐chain engineering on the ladder‐type core is employed. Three SMAs named BTTIC‐Th, BTTIC‐TT, and BTTIC‐Ph with thiophene, thieno[3,2‐b]thiophene, and benzene, respectively, as side chains, are designed and synthesized. Three SMAs exhibit similar absorption ranges but different lowest unoccupied molecular orbital (LUMO) energy levels due to the different strength of the δ‐inductive effect between vertical aromatic side chains and their electron‐rich core. Organic solar cells based on PBDB‐T:BTTIC‐TT achieve a power conversion efficiency (PCE) of 13.44%, which is higher than the PCE of devices based on PBDB‐T:BTTIC‐Th (12.91%) and PBDB‐T:BTTIC‐Ph (9.14%). The difference in device performance is investigated by electrical and morphological characterizations. A large domain size and different types of π–π stacking are found in the bulk heterojunction layer of PBDB‐T:BTTIC‐Ph blend film, which are detrimental to exciton dissociation and charge transport. Overall, it is demonstrated that when designing unconjugated side chains, thieno[3,2‐b]thiophene is superior to thiophene and benzene through its dual roles of promoting the LUMO energy level and optimizing the morphology. These results shed light on the side‐chain engineering of high‐performance non‐fullerene SMAs.     

Impact of the Nature of the Side‐Chains on the Polymer‐Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

Polymer‐fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton‐dissociation, charge‐separation, and charge‐recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side‐chains on the polymer‐fullerene packing in mixed regions. The focus is on poly‐benzo[1,2‐b:4,5‐b′]dithiophene‐thieno[3,4‐c]pyrrole‐4,6‐dione (PBDTTPD) as electron‐donating material and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) as electron‐accepting material. Three polymer side‐chain patterns are considered: i) linear side‐chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side‐chains on BDT and a branched side‐chain on TPD; and iii) two branched side‐chains on BDT and a linear side‐chain on TPD. Increasing the number of branched side‐chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC₆₁ BM mixing. The nature and location of side‐chains are found to play a determining role in the probability of finding PC₆₁BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton‐dissociation and charge‐recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC₆₁BM solar‐cell performance as a function of side‐chain patterns.     

Massive Anisotropic Thermal Expansion and Thermo‐Responsive Breathing in Metal–Organic Frameworks Modulated by Linker Functionalization

Functionalized metal–organic frameworks (fu‐MOFs) of general formula [Zn₂(fu‐L)₂dabco]_n show unprecedentedly large uniaxial positive and negative thermal expansion (fu‐L = alkoxy functionalized 1,4‐benzenedicarboxylate, dabco = 1,4‐diazabicyclo[2.2.2]octane). The magnitude of the volumetric thermal expansion is more comparable to property of liquid water rather than any crystalline solid‐state material. The alkoxy side chains of fu‐L are connected to the framework skeleton but nevertheless exhibit large conformational flexibility. Thermally induced motion of these side chains induces extremely large anisotropic framework expansion and eventually triggers reversible solid state phase transitions to drastically expanded structures. The thermo‐responsive properties of these hybrid solid–liquid materials are precisely controlled by the choice and combination of fu‐Ls and depend on functional moieties and chain lengths. In principle, this combinatorial approach allows for a targeted design of extreme thermo‐mechanical properties of MOFs addressing the regime between crystalline solid matter and the liquid state.     

Photoresponsive Ferroelectric Liquid‐Crystalline Polymers

The photoresponse of ferroelectric smectic side‐chain liquid‐crystalline (LC) polymers containing a photoisomerizable azobenzene derivative as a covalently linked photochromic side group is investigated. By static measurements in different photostationary states, the effect of trans–cis isomerization on the material's phase‐transition temperatures and its ferroelectric properties (spontaneous electric polarization P_S and director tilt angle θ) are analyzed. It turns out that the Curie temperature (transition S_C* to S_A) can be reversibly shifted by up to 17 °C. The molecular mechanism of this “photoferroelectric effect” is studied in detail using time‐resolved measurements of the dye's optical absorbance, the director tilt angle, and the spontaneous polarization, which show a direct response of the ferroelectric parameters to the molecular isomerization. The kinetics of the thermal reisomerization of the azo dye in the LC matrix are evaluated. A comparison to the reisomerization reaction in isotropic solution (toluene) reveals a faster thermal relaxation of the dye in the LC phase.     

Alternating Copolymers of Cyclopenta[2,1‐b;3,4‐b′]dithiophene and Thieno[3,4‐c]pyrrole‐4,6‐dione for High‐Performance Polymer Solar Cells

A series of alternating copolymers of cyclopenta[2,1‐b;3,4‐b′]dithiophene (CPDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) have been prepared and characterized for polymer solar cell (PSC) applications. Different alkyl side chains, including butyl (Bu), hexyl (He), octyl (Oc), and 2‐ethylhexyl (EH), are introduced to the TPD unit in order to adjust the packing of the polymer chain in the solid state, while the hexyl side chain on the CPDT unit remains unchanged to simplify discussion. The polymers in this series have a simple main chain structure and can be synthesized easily, have a narrow band gap and a broad light absorption. The different alkyl chains on the TPD unit not only significantly influence the solubility and chain packing, but also fine tune the energy levels of the polymers. The polymers with Oc or EH group have lower HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy levels, resulting higher open circuit voltages (V_oc) of the PSC devices. Power conversion efficiencies (PCEs) up to 5.5% and 6.4% are obtained from the devices of the Oc substituted polymer (PCPDTTPD‐Oc) with PC₆₁BM and PC₇₁BM, respectively. This side chain effect on the PSC performance is related to the formation of a fine bulk heterojunction structure of polymer and PCBM domains, as observed with atomic force microscopy.     

Efficient Polymer Solar Cells with a High Open Circuit Voltage of 1 Volt

A series of polymers containing benzo[1,2‐b:4,5‐b′]dithiophene and N‐alkylthieno[3,4‐c]pyrrole‐4,6‐dione are designed. By incorporating different alkylthienyl side chains, the fill factor (FF) and open circuit voltage (V_oc) of the copolymers are further improved. The experimental results and theoretical calculations show that the size and topology of the side chains can influence the polymer solubility, energy levels, and intermolecular packing by altering the molecular coplanarity. As a result of improved morphology and fine‐tuned energy levels, an increased FF and a high V_oc of 1.00 V are achieved, as well as a power conversion efficiency of 6.17%, which is the highest efficiency ever reported for polymer solar cells with a V_oc over 1 V.     

Optically Tunable Field Effect Transistors with Conjugated Polymer Entailing Azobenzene Groups in the Side Chains

Semiconducting conjugated polymers with photoswitching behavior are highly demanded for field‐effect transistors (FETs) with tunable electronic properties. Herein a new design strategy is established for photoresponsive conjugated polymers by incorporating photochromic units (azobenzene) into the flexible side alkyl chains. It is shown that azobenzene groups in the side chains of the DPP (diketopyrrolopyrrole)‐quaterthiophene polymer ( PDAZO ) can undergo trans/cis photoisomerization in fully reversible and fast manner. Optically tunable FETs with bistable states are successfully fabricated with thin films of PDAZO . The drain‐source currents are reduced by 80.1% after UV light irradiation for ≈28 s, which are easily restored after further visible light irradiation for ≈33 s. Such fast optically tunable FETs are not reported before. Moreover, such current photomodulation can be implemented for multiple light irradiation cycles with good photofatigue resistance. Additionally, thin film charge mobility of PDAZO can be reversibly modulated by alternating UV and visible light irradiations. On the basis of theoretical calculations and GIWAXS data, it is hypothesized that the dipole moment and configuration changes associated with the trans‐/cis‐photoisomerization of azobenzene groups in PDAZO can affect the respective intra‐chain and inter‐chain charge transporting, which is responsible for the optically tunable behavior for FETs with thin films of PDAZO .     

Proton‐Conducting Aromatic Polymers Carrying Hypersulfonated Side Chains for Fuel Cell Applications

Polysulfone main chains have been functionalized with hypersulfonated aromatic side chains where the sulfonic acid groups were highly concentrated on a local scale, with two acid groups placed on the same aromatic ring. This molecular design was implemented to promote the nanophase separation that takes place in proton‐exchange membranes between the hydrophobic polymer main chain and the hydrophilic ionic groups responsible for the water uptake and conduction. Morphological investigations revealed that polysulfones functionalized with disulfonaphthoxybenzoyl or trisulfopyrenoxybenzoyl side chains contained larger and more uniform ionic clusters, as compared to conventionally sulfonated polysulfones where the acid groups are dispersed along the main chain. Membranes based on the polymers carrying hypersulfonated side chains formed efficient networks of water‐filled nanopores upon hydration, which facilitated excellent levels of proton conductivity exceeding that of the commercial Nafion membrane at moderate water uptakes.     

Structure Tuning of Crown Ether Grafted Conjugated Polymers as the Electron Transport Layer in Bulk‐Heterojunction Polymer Solar Cells for High Performance

A series of novel electron transport (ET) polymers composed of different conjugated main chains (fluorene, thiophene, and 2,7‐carbazole) and crown ether side chain (crown ether, aza‐crown ether and amine) is presented for bulk‐heterojunction polymer solar cells with poly(3‐hexylthiophene) (P3HT) or poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo [1,2‐b:4,5‐b′] dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]](PTB7) as the active polymer and aluminum metal as the cathode. Unexpectedly, it is found that the main chain of ET polymers has a greater effect on the interfacial dipole than the side chain, even when attaching a high polarity group. The electron‐rich bridge atom of the main chain may also contribute appreciably to the interfacial dipole. When used as the ET layer, all of these polymers can generate an optical interference effect for redistribution of the optical electric field as an optical spacer and, therefore, allow more light to be absorbed by the active layer, thus leading to an increase in short‐circuit current density. They can also block hole diffusion to the cathode and prevent electron–hole recombination during the ET process. Among the five ET polymers investigated, PCCn6 is the most effective one, providing a remarkable improvement in the power conversion efficiency (measured in air) of the device to 8.13% compared to 5.20% for PTB7:[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM).     

Bimolecular Crystals of Fullerenes in Conjugated Polymers and the Implications of Molecular Mixing for Solar Cells

The performance of polymer:fullerene bulk heterojunction solar cells is heavily influenced by the interpenetrating nanostructure formed by the two semiconductors because the size of the phases, the nature of the interface, and molecular packing affect exciton dissociation, recombination, and charge transport. Here, X‐ray diffraction is used to demonstrate the formation of stable, well‐ordered bimolecular crystals of fullerene intercalated between the side‐chains of the semiconducting polymer poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene. It is shown that fullerene intercalation is general and is likely to occur in blends with both amorphous and semicrystalline polymers when there is enough free volume between the side‐chains to accommodate the fullerene molecule. These findings offer explanations for why luminescence is completely quenched in crystals much larger than exciton diffusion lengths, how the hole mobility of poly(2‐methoxy‐5‐(3′,7′‐dimethyloxy)‐p‐phylene vinylene) increases by over 2 orders of magnitude when blended with fullerene derivatives, and why large‐scale phase separation occurs in some polymer:fullerene blend ratios while thermodynamically stable mixing on the molecular scale occurs for others. Furthermore, it is shown that intercalation of fullerenes between side chains mostly determines the optimum polymer:fullerene blending ratios. These discoveries suggest a method of intentionally designing bimolecular crystals and tuning their properties to create novel materials for photovoltaic and other applications.     

Optimization of Solubility,Film Morphology and Photodetector Performance by Molecular Side‐Chain Engineering of Low‐Bandgap Thienothiadiazole‐Based Polymers

A series of donor–acceptor (D‐A) type low‐bandgap polymers containing the terthiophene and thieno[3,4‐b]thiadiazole units in the main chain but different numbers of identical side chains are designed and synthesized in order to study the effect of side chain on the polymer properties and optimize the performance of polymer photodetectors. Variation in the side chain content can influence the polymer solubility, molecular packing, and film morphology, which in turn affects the photodetector performance, particularly with regard to the photoresponsivity and dark current. X‐ray diffraction patterns indicate that molecular ordering increases with more side chains. Atomic force microscopy shows that appropriate morphology of the active layer in the polymer photodetector is necessary for high photocurrent and low dark current. Using BCP as a hole blocking layer (10 nm), the photodetector based on P4 exhibits the optimized performance with specific detectivity of 1.4 × 10¹² Jones at 800 nm, which is among the best reported values for polymer photodetectors and even comparable to that of a silicon photodetector.     

Side chain engineering: The effect on the properties of isoindigo-based conjugated polymers contain different length and structure alkyl chains on nitrogen atom

A series of donor-acceptor (D-A) conjugated polymers based on benzo[1,2-b:4,5-b’]dithiophene (BDT) and isoindigo with different alkyl side chains were designed and synthesized. These polymers named PBDT-TT-IID_O, PBDT-TT-IID_EH, PBDT-TT-IID_BO, PBDT-TT-IID_HD, and PBDT-TT-IID_OD have different length or structure of the alkyl side chains on isoindigo unit. As the length of the alkyl chain increases, the solubility of the polymer enhances. The results indicate that the alkyl side chains have little effect on the optical properties of individual polymer molecules, but have a significant impact on optical, electrochemical, film-forming and photovoltaic properties of the polymers in the aggregated state. PBDT-TT-IID_HD with a sixteen carbon branched chain achieves the best power conversion efficiencies (PCEs) of 6.83% when blending with [6,6]-phenyl C71 butyric acid methyl ester (PC₇₁BM) as acceptor. The influence of the alkyl side chain on the short-circuit current is much greater than that of the open circuit voltage. Atomic force microscopy (AFM) reveals that the side chains changed the morphology of the active layers and the size of the phase region. For isoindigo based polymers, hexyl-decyl group in the commonly used alkyl chains appear to be a good choice.