Ladder-type Polymer Research Articles

Ladder-Type Redox-Active Polymer Achieves Ultra-stable and Fast Proton Storage in Aqueous Proton Batteries.

Affordable and safe aqueous proton batteries (APBs) with unique "Grotthuss mechanism," are very significant for advancing carbon neutrality initiatives. While organic polymers offer a robust and adaptable framework that is well-suited for APB electrodes, the limited proton-storage redox capacity has constrained their broader application. Herein, a ladder-type polymer (PNMZ) has been designed via a covalent cycloconjugation conformational strategy that exhibits optimized electronic structure and fast intra-chain charge transport within the high-aromaticity polymeric skeleton. As a result, the polymer exhibits exceptional proton-storage redox kinetics, which are evidenced by in-operando monitoring techniques and theoretical calculations. It achieves a remarkable proton-storage capacity of 189 mAh g-1 at 2 A g-1 and excellent long-term cycling stability, with approximately 97.8% capacity retention over 10,000 cycles. Finally, a high-performance all-polymer APB device has been successfully constructed with a desirable capacity retention of 99.7% after 6,000 cycles and high energy density of 56.3 Wh kg-1.

Wavy Graphene Nanoribbons Containing Periodic Eight-Membered Rings for Light-Emitting Electrochemical Cells.

Precision graphene nanoribbons (GNRs) offer distinctive physicochemical properties that are highly dependent on their geometric topologies, thereby holding great potential for applications in carbon-based optoelectronics and spintronics. While the edge structure and width control has been a popular strategy for engineering the optoelectronic properties of GNRs, non-hexagonal-ring-containing GNRs remain underexplored due to synthetic challenges, despite offering an equally high potential for tailored properties. Herein, we report the synthesis of a wavy GNR (wGNR) embedding periodic eight-membered rings into its carbon skeleton, which is achieved by the A2B2-type Diels-Alder polymerization between dibenzocyclooctadiyne (6) and dicyclopenta[e,l]pyrene-5,11-dione derivative (8), followed by a selective Scholl reaction of the obtained ladder-type polymer (LTP) precursor. The obtained wGNR, with a length of up to 30 nm, is thoroughly characterized by solid-state NMR, FT-IR, Raman, and UV-Vis spectroscopy with the support of DFT calculations. The non-planar geometry of wGNR efficiently prevents the inter-ribbon π-π aggregation, leading to photoluminescence in solution. Consequently, the wGNR can function as an emissive layer for organic light-emitting electrochemical cells (OLECs), offering a proof-of-concept exploration in implementing luminescent GNRs into optoelectronic devices. The fast-responding OLECs employing wGNR will pave the way for advancements in OLEC technology and other optoelectronic devices.

Temporal mode switching during polariton condensation

Multimode behavior plays a key role in a wide range of nonlinear optical phenomena. Multiple exciton-polariton modes can attain macroscopic population as observed in time-integrated measurements. Recent theory work has shown that, rather than being simultaneously in many modes, the population may temporally switch between the modes. However, the origin and the dynamics of multimode condensation has not been experimentally addressed. Here, we study the dynamics of exciton-polariton condensation into multiple modes of Gaussian defect microcavities filled with ladder type polymer gain material methyl-substituted ladder-type poly(p-phenylene) MeLPPP. We deploy a second-order cumulant model to simulate the dynamics of the system and find picosecond-timescale switching between condensate modes. By interferometric measurements we reveal the experimental signatures of such mode competition behaviour.

High-capacity potassium-ion batteries using new rigid backbone quinone-based polymer electrode materials

We report the synthesis and electrochemical study of three quinone-based ladder-type redox-active polymers. These materials were applied as electrode materials in potassium half-cells and delivered high specific discharge capacities of up to 268 mAh g−1 at 0.66 A g−1. Using concentrated diglyme-based electrolyte formulation allowed us to suppress capacity fading and enable stable charge-discharge cycling of the batteries. The designed materials represent promising electrode materials for emerging scalable organic potassium-ion battery technology.

Ion-tunable antiambipolarity in mixed ion–electron conducting polymers enables biorealistic organic electrochemical neurons

Biointegrated neuromorphic hardware holds promise for new protocols to record/regulate signalling in biological systems. Making such artificial neural circuits successful requires minimal device/circuit complexity and ion-based operating mechanisms akin to those found in biology. Artificial spiking neurons, based on silicon-based complementary metal-oxide semiconductors or negative differential resistance device circuits, can emulate several neural features but are complicated to fabricate, not biocompatible and lack ion-/chemical-based modulation features. Here we report a biorealistic conductance-based organic electrochemical neuron (c-OECN) using a mixed ion–electron conducting ladder-type polymer with stable ion-tunable antiambipolarity. The latter is used to emulate the activation/inactivation of sodium channels and delayed activation of potassium channels of biological neurons. These c-OECNs can spike at bioplausible frequencies nearing 100 Hz, emulate most critical biological neural features, demonstrate stochastic spiking and enable neurotransmitter-/amino acid-/ion-based spiking modulation, which is then used to stimulate biological nerves in vivo. These combined features are impossible to achieve using previous technologies.

A tetrathienopyrrole-based ladder-type donor polymer for high-performance organic near-infrared cavity detectors.

Organic semiconductors can afford detection at wavelengths beyond commercial silicon photodetectors. However, for each targeted near-infrared wavelength range, this requires individually optimized materials, which adds to the complexity and costs. Moreover, finding molecules with strong absorption beyond 1 μm that perform well in organic photodetectors remains a challenge. In microcavity devices, the detection window can be extended to wavelengths inaccessible for silicon without the need for new materials by adopting an intelligent design. Previous work has demonstrated the applicability of a dithienopyrrole-based donor polymer (PDTPQx) in such a cavity photodetector device, with a photoresponse up to 1200 nm. In this work, the π-conjugated backbone of the polymer is extended, affording higher hole mobility and better donor:acceptor intermixing. This leads to enhanced peak external quantum efficiencies up to 1450 nm. The (thermal noise limited) detectivities achieved with the PTTPQx polymer (1.07 × 1012 to 1.82 × 1010 Jones) are among the very best in the 900-1400 nm wavelength regime.

Structural influence of the length and functionality of N,N-donor spacers in Cd(II) ladder-type coordination polymers

The understanding of the effect generated by small differences of the organic ligands on the molecular and supramolecular arrangement of coordination polymers (CPs) is a key factor to control their properties. Therefore, the study of structurally related ligands differing in some factors inter alia functional group orientation, length, or functionality is a crucial task for crystal engineers. In this contribution, the reactions between Cd(OAc)2·2H2O, α-acetamidocinnamic acid (HACA) and different N,N-donor spacers with increasing length (pyrazine, pyz; 4,4’-bipyridine, 4,4’-bipy; 1,2-bis(4-pyridyl)ethylene, 1,2-bpe), as well as additional functionalities (4,4’-azopyridine, 4,4’-azpy) have been successfully performed. Their crystal structures have been elucidated revealing a family of ladder-type 1D CPs showing molecular arrays with single pillars for {[Cd2(μ-ACA)2(ACA)2(pyz)(H2O)2]·2EtOH}n (1), and double pillars for [Cd2(μ-ACA)2(ACA)2(4,4’-bipy)2]n (2), [Cd2(μ-ACA)2(ACA)2(1,2-bpe)2]n (3) and {[Cd2(μ-ACA)2(ACA)2(4,4’-azpy)2]·4,4’-azpy·9H2O}n (4). Remarkably, the effect of the addition of the azo group in 4 compared with 2 and 3 has led to a CP with the same molecular arrangement but different crystal packing, allowing the introduction of one non-coordinated 4,4’-azpy and nine water molecules. Finally, their solid-state UV-Vis and photoluminescence have been measured observing their blue-emitting properties.

All-Polymer Bulk-Heterojunction Organic Electrochemical Transistors with Balanced Ionic and Electronic Transport.

The rapid development of organic electrochemical transistor (OECTs)-based circuits brings new opportunities for next-generation integrated bioelectronics. The all-polymer bulk-heterojunction (BHJ) offers an attractive, inexpensive alternative to achieve efficient ambipolar OECTs, and building blocks of logic circuits constructed from them, but have not been investigated to date. Here, the first all-polymer BHJ-based OECTs are reported, consisting of a blend of new p-type ladder conjugated polymer and a state-of-the-art n-type ladder polymer. The whole ladder-type polymer BHJ also proves that side chains are not necessary for good ion transport. Instead, the polymer nanostructures play a critical role in the ion penetration and transportation and thus in the device performance. It also provides a facile strategy and simplifies the fabrication process, forgoing the need to pattern multiple active layers. In addition, the development of complementary metal-oxide-semiconductor (CMOS)-like OECTs allows the pursuit of advanced functional logic circuitry, including inverters and NAND gates, as well as for amplifying electrophysiology signals. This work opens a new approach to the design of new materials for OECTs and will contribute to the development of organic heterojunctions for ambipolar OECTs toward high-performing logic circuits.

Synthesis of Ladder-Type 9,9'-Bifluorenylidene-Based Conjugated Oligomers via a Pd-Catalyzed Tandem Suzuki Coupling/Heck Cyclization Approach.

For new ladder-type oligomers and polymers with versatile and robust synthetic strategies, in this study, four fully conjugated ladder-type overcrowded 9,9'-bifluorenylidene-based compounds and oligomers (BFY1, BFY2, BFY3, and BFY4) were synthesized via a Pd-catalyzed tandem Suzuki coupling/Heck cyclization reaction. By monomer screening and route optimization, the target products were obtained in high yields and characterized by 1H and 13C NMR spectroscopy and high resolution mass spectroscopy.

Conjugated ladder-type polymers with multielectron reactions as high-capacity organic anode materials for lithium-ion batteries

Ladder-type conjugated polymers (LCPs) have attracted extensive attention in rechargeable lithium-ion batteries (LIBs) due to their inherent stability, poor solubility, tunable structure, and strong π—π intermolecular interactions. Herein, we describe the synthesis of two heteroatom nitrogen/oxygen-rich LCPs (TABQ-NTCDA, named TNL, and TABQ-PMDA, named TPL) by the polycondensation reaction of tetromino-benzoquinone (TABQ) and aromatic dianhydride. Benefiting from the rigid backbone, the large conjugated skeleton and the heteroatom-driven superlithiation process in polycyclic aromatic systems, heteroatom nitrogen/oxygen-rich LCPs acting as organic anode materials for LIBs display high specific capacity and long-term cycle stability. In particular, TNL displays a high reversible capacity of 1063.5 mA h g−1 at 0.05 A g−1, good cyclic performance with a capacity retention of 75.2% after 1000 cycles at 1 A g−1, and excellent rate capability of 260.6 mA h g−1 even at 2 A g−1. In addition, the superlithiation storage mechanism was further confirmed by theoretical calculations, suggesting multiple active sites of C=O, C=N, and aromatic rings for lithium-ion storage. Furthermore, a full cell is also assembled by pairing a TNL anode with a LiCoO2 cathode, indicating the feasibility of practical application.

Quinone-Based Ladder-Type Polymers as Promising Electrode Materials for Potassium-Ion Batteries

Quinone-Based Ladder-Type Polymers as Promising Electrode Materials for Potassium-Ion Batteries

Influence of Molecular Weight on the Organic Electrochemical Transistor Performance of Ladder-Type Conjugated Polymers.

Organic electrochemical transistors (OECTs) hold promise for developing a variety of high-performance (bio-)electronic devices/circuits. While OECTs based on p-type semiconductors have achieved tremendous progress in recent years, n-type OECTs still suffer from low performance, hampering the development of power-efficient electronics. Here, it is demonstrated that fine-tuning the molecular weight of the rigid, ladder-type n-type polymer poly(benzimidazobenzophenanthroline) (BBL) by only one order of magnitude (from 4.9 to 51kDa) enables the development of n-type OECTs with record-high geometry-normalized transconductance (gm,norm ≈ 11 S cm-1 ) and electron mobility × volumetric capacitance (µC* ≈ 26 F cm-1 V-1 s-1 ), fast temporal response (0.38ms), and low threshold voltage (0.15V). This enhancement in OECT performance is ascribed to a more efficient intermolecular charge transport in high-molecular-weight BBL than in the low-molecular-weight counterpart. OECT-based complementary inverters are also demonstrated with record-high voltage gains of up to 100V V-1 and ultralow power consumption down to 0.32 nW, depending on the supply voltage. These devices are among the best sub-1 Vcomplementary inverters reported to date. These findings demonstrate the importance of molecular weight in optimizing the OECT performance of rigid organic mixed ionic-electronic conductors and open for a new generation of power-efficient organic (bio-)electronic devices.

Single-photon nonlinearity at room temperature.

The recent progress in nanotechnology1,2 and single-molecule spectroscopy3-5 paves the way foremergent cost-effective organic quantum optical technologies with potential applications in useful devices operating at ambient conditions. We harness a π-conjugated ladder-type polymer strongly coupled to a microcavity forming hybrid light-matter states, so-called exciton-polaritons, to create exciton-polariton condensates with quantum fluid properties. Obeying Bose statistics, exciton-polaritons exhibit an extreme nonlinearity when undergoing bosonic stimulation6, which we have managed to trigger at the single-photon level, thereby providing an efficient way for all-optical ultrafast control over the macroscopic condensate wavefunction. Here, we utilize stable excitons dressed with high-energy molecular vibrations, allowing for single-photon nonlinear operation at ambient conditions. This opens new horizons for practical implementations like sub-picosecond switching, amplification and all-optical logic at the fundamental quantum limit.

Conjugated Ladder-Type Polymer with Hexaazatriphenylene Units as a Cathode Material for Lithium, Sodium, and Potassium Batteries

Conjugated Ladder-Type Polymer with Hexaazatriphenylene Units as a Cathode Material for Lithium, Sodium, and Potassium Batteries

Recent Advances in Molecular Design of Organic Thermoelectric Materials

Recent Advances in Molecular Design of Organic Thermoelectric Materials

Synthesis of Symmetric Conjugated Ladder-Type Polymers with Nitrogen Bridges

Synthesis of Symmetric Conjugated Ladder-Type Polymers with Nitrogen Bridges

Pair of chiral molecular ladders and successive hydration in single-crystal-to-single-crystal mode

Self-assembly of Zn(NO3)2 with a pair of new tridentate chiral Ls produced a pair of chiral ladder-type 1D coordination polymers, where crystals were transformed into different hydrated products of zigzag 1Ds depending on chirality in the SCSC mode.

The Chemistry and Applications of Heteroisoindigo Units as Enabling Links for Semiconducting Materials.

ConspectusBecause of their low-temperature processing properties and inherent mechanical flexibility, semiconducting materials are promising candidates for enabling flexible displays, renewable energy, biological sensors, and healthcare. Progress has been made in materials performance by developing judicious materials design strategies. For example, improvements in electron transport have required new electron-deficient aromatics. Among them, isoindigo (IID) is an important functional group utilized in conjugated aromatics, where the structure combines two sets of five-membered electron-withdrawing lactam rings, exhibiting enhanced solubility, excellent chemical and thermal stabilities, broad absorption, and intriguing electron affinity.In the past decade, researchers have mainly focused on IID-based materials. However, the effect of heteroatom modification of the IID core has rarely been systemically investigated. In conventional conjugated polymers, single bonds connect the monomers, leading to energetic disorder and torsion defects, while ladder-type polymers are often intractable because of their fused nature. In this regard, the molecular design of new π scaffolds based on IID is central to the development of high-performance semiconductor polymers. Especially, a complete refresh of molecular design strategies and novel conjugated polymers with unique structures are needed to circumvent the disadvantages of the conventional ladder-type polymers.In this Account, we systematically summarize our recent progress in the design, synthesis, and structure-property relationships of IID- and particularly hetero-IID-based functional materials. More specifically, starting with molecular engineering of hetero-IIDs with variable electronic effects, conjugation lengths, and numbers of heterorings, we discuss the effect of the heteroring on the absorption spectra and energy levels. Additionally, we investigate a series of electron-withdrawing substitution of IIDs and hetero-IIDs and their molecular self-assembly behavior and the device performance. Furthermore, we discuss a series of IID-bis(EDOT) copolymers with hydrophilic ethylene glycol side chains for accumulation-mode organic thin-film electrochemical transistors, in which the relationships among the molecular structure, operational stability, film morphology, and device performance were revealed. Compared with IID polymers, the HOMO levels and optical band gaps of the thiophene and thienothiophene IID copolymers markedly decrease, and these polymers exhibit ambipolar charge transport. When we further expanded the IID core to a thieno[3,2-b][1]benzothiophene isoindigo (TBTI) core, such as in TBTIT, bulk-heterojunction solar cells employing this polymer class as the electron donor achieved good efficiency for additive- and annealing-free device conditions. When we introduced electron-deficient pyridine on the IID core, both the LUMO and HOMO energy levels of the copolymers markedly decreased, which significantly improved the electron mobility. In addition, we compare the correlation between the polymer structures of IID and hetero-IID copolymers with thiophene and benzothiophene as comonomers and their absorption spectra and energy levels. In particular, we evaluate the planarity and the dihedral angle between the repeat units, with systematic analysis by theoretical calculations to support our design concepts. We discuss polymer designs arising from simple aldol condensation, where the rigid backbone conformation has been locked by the double bonds. Our polymers display broad absorption from the visible to the NIR-II region, and more importantly, the high electron affinities of these polymers provide a platform to realize ambient-stable electron transport in solution-processed organic thin-film transistors. These exciting results are expected to open doors to new horizons of semiconducting materials in terms of other charming applications and the design and synthesis of superior materials.

Sequential Doping of Ladder-Type Conjugated Polymers for Thermally Stable n-Type Organic Conductors.

Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable. Here, we report on the sequential doping of the ladder-type polymer poly(benzimidazobenzophenanthroline) (BBL) with a benzimidazole-based dopant (i.e., N-DMBI). By combining electrical, UV–vis/infrared, X-ray diffraction, and electron paramagnetic resonance measurements, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and microstructure of the sequentially doped polymer films as a function of the thermal annealing temperature. Importantly, we observed that the electrical conductivity of N-DMBI-doped BBL remains unchanged even after 20 h of heating at 190 °C. This finding is remarkable and of particular interest for organic thermoelectrics.

A new ladder-type silver(I) coordination polymer with 4,4'-bipyridine and 4-[(4-carboxybenzyloxy)methyl]benzoate ligands: synthesis, crystal structure, fluorescence properties and Hirshfeld surface analysis.

A novel ladder-type coordination polymer (CP), poly[(μ-4,4'-bipyridine-κ2N:N'){μ-4-[(4-carboxybenzyloxy)methyl]benzoato-κO}silver(I)](Ag-Ag), [Ag(C16H13O5)(C10H8N2)]n or [Ag(HL)(4,4'-bpy)]n {H2L is 4,4'-[oxybis(methylene)]dibenzoic acid and 4,4'-bpy is 4,4'-bipyridine}, was synthesized using hydrothermal methods. The complex was characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction, and is a ladder-type CP which exhibits an obvious Ag-Ag interaction. The legs of the ladder are formed by parallel 4,4'-bipy ligands and silver ions, and the rungs are constructed by Ag-Ag interactions. A Hirshfeld surface analysis was carried out and is discussed in detail. The complex also displays favourable fluorescence properties.