Exciton polaron formation and hot-carrier relaxation in rigid Dion-Jacobson-type two-dimensional perovskites.

The efficiency of two-dimensional Dion-Jacobson-type materials relies on the complex interplay between electronic and lattice dynamics; however, questions remain about the functional role of exciton-phonon interactions. Here we establish the robust polaronic nature of the excitons in these materials at room temperature by combining ultrafast spectroscopy and electronic structure calculations. We show that polaronic distortion is associated with low-frequency (30-60 cm-1) lead iodide octahedral lattice motions. More importantly, we discover how targeted ligand modification of this two-dimensional perovskite structure manipulates exciton-phonon coupling, exciton polaron population and carrier cooling. At high excitation density, stronger exciton-phonon coupling increases the hot-carrier lifetime, forming a hot-phonon bottleneck. Our study provides detailed insight into the exciton-phonon coupling and its role in carrier cooling in two-dimensional perovskites relevant for developing emerging hybrid semiconductor materials with tailored properties.

Blade Coating Poly(3-hexylthiophene): The Importance of Molecular Weight on Thin-Film Microstructures.

Poly(3-hexylthiophene) is one of the most prevalent and promising conjugated polymers for use in organic electronics. However, the deposition of this material in thin films is highly dependent on the process, such as blade coating versus spin coating and material properties such as molecular weight. Typically, large polymer dispersity makes it difficult to isolate the effect of molecular weight without considering a distribution. In this study, we characterize oligothiophenes of exactly 8, 11, and 14 repeat units, which were deposited into thin films by varying blade coating conditions and postdeposition annealing. From synchrotron-based grazing incidence wide-angle X-ray scattering (GIWAXS), scanning transmission X-ray microscopy (STXM) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), Raman microscopy, optical microscopy, and X-ray diffraction (XRD), it was suggested that higher molecular weight polymers exhibit a fast-forming crystalline polymorph (form-1) while low molecular weight polymers exhibit a slow forming polymorph (form-2) with large domain boundaries. As molecular weight is gradually increased, the polymorph formed transitions from form-1 and form-2, where 11 repeat unit oligomers display both polymorphs. We also found that processing conditions can increase the formation of the form-2 polymorph. We also report improved organic thin film transistor (OTFT) performance when form-1 is present. Overall, oligothiophene polymorph formation is highly dependent on the molecular weight and processing conditions, providing critical insight into the importance of polymer weight control in the development of thin-film electronics based on conjugated polymers.

Sequence-Defined Conjugated Oligomers in Donor-Acceptor Dyads.

Conjugated macromolecules have a rich history in chemistry, owing to their chemical arrangements that intertwine physical and electronic properties. The continuing study and application of these systems, however, necessitates the development of atomically precise models that bridge the gap between molecules, polymers, and/or their blends. One class of conjugated polymers that have facilitated the advancement of structure-property relationships is discrete, precision oligomers that have remained an outstanding synthetic challenge with only a handful of reported examples. Here we show the first synthesis of molecular dyads featuring sequence-defined oligothiophene donors covalently linked a to small-molecule acceptor. These dyads serve as a platform for probing complex photophysical interactions involving sequence-defined oligomers. This assessment is facilitated through the unprecedented control of oligothiophene length- and sequence-dependent arrangement relative to the acceptor unit, made possible by the incorporation of hydroxyl-containing side chains at precise positions along the backbone through sequence-defined oligomerizations. We show that both the oligothiophene sequence and length play complementary roles in determining the transfer efficiency of photoexcited states. Overall, the work highlights the importance of the spatial arrangement of donor-acceptor systems that are commonly studied for a range of uses, including light harvesting and photocatalysis.

Influence of Backbone on the Performance of Pendant Polymer Electrode Materials in Li-ion Batteries.

Pendant polymers are a promising class of electrode materials due to their synthetic simplicity, derivation from sustainable feedstocks, and potentially benign synthesis. These materials consist of a redox-active pendant tethered to a polymer backbone, which mitigates dissolution during electrode cycling. To date, an extensive number of pendant groups have been studied within the context of metal-ion batteries. However, the choice of the polymer backbone and its impact on the electrode performance have been relatively understudied. In this work, we use a postpolymerization modification approach to synthesize a series of viologen-bearing redox-active pendant polymers with similar molecular weights but three distinct chemical backbones, namely, polyacrylamide, polymethacrylamide, and polystyryl. By evaluating the polymers in lithium-ion batteries, we show that the polymer backbone has a significant influence on electrode performance and behavior. Specifically, the polymethacrylamide displays slower kinetics than the other two polymers, resulting in lower capacities, particularly at high cycling rates. Furthermore, the charge storage mechanism is dependent on the nature of the backbone: the polyacrylamide shows a significant capacitive contribution to charge storage, while the polystyryl does not. The difference in performance between the polymer electrode materials is ascribed to a difference in chain mobility and packing within the electrode films. Overall, this work shows that the fundamental properties of the polymer backbone are critical to the design of high-performance polymer electrodes.

Large piezoelectric response in a Jahn-Teller distorted molecular metal halide.

Piezoelectric materials convert between mechanical and electrical energy and are a basis for self-powered electronics. Current piezoelectrics exhibit either large charge (d33) or voltage (g33) coefficients but not both simultaneously, and yet the maximum energy density for energy harvesting is determined by the transduction coefficient: d33*g33. In prior piezoelectrics, an increase in polarization usually accompanies a dramatic rise in the dielectric constant, resulting in trade off between d33 and g33. This recognition led us to a design concept: increase polarization through Jahn-Teller lattice distortion and reduce the dielectric constant using a highly confined 0D molecular architecture. With this in mind, we sought to insert a quasi-spherical cation into a Jahn-Teller distorted lattice, increasing the mechanical response for a large piezoelectric coefficient. We implemented this concept by developing EDABCO-CuCl4 (EDABCO = N-ethyl-1,4-diazoniabicyclo[2.2.2]octonium), a molecular piezoelectric with a d33 of 165 pm/V and g33 of ~2110 × 10-3 V m N-1, one that achieved thusly a combined transduction coefficient of 348 × 10-12 m3 J-1. This enables piezoelectric energy harvesting in EDABCO-CuCl4@PVDF (polyvinylidene fluoride) composite film with a peak power density of 43 µW/cm2 (at 50 kPa), the highest value reported for mechanical energy harvesters based on heavy-metal-free molecular piezoelectric.

Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation.

Considering nearly infinite design possibilities, organic second harmonic generation (SHG) molecules are believed to have long-term promise. However, because of the tendency to form dipole-antiparallel crystals that lead to zero macroscopic polarization, it is difficult to design a nonlinear optical (NLO) material based on organic molecules. In this manuscript, we report a new molecule motif that can form asymmetric organic solids by controlling the degree of hydrogen bonding through protonation. A conjugated polar organic molecule was prepared with a triple bond connecting an electron-withdrawing pyridine ring and an electron-donating thiophene ring. By controlling the degree of hydrogen bonding through protonation, two different crystal packing motifs are achieved. One crystallizes into the common dipole-antiparallel nonpolar P1̄ space group. The second crystallizes into the uncommon dipole-parallel polar P1 space group, in which the molecular dipoles are aligned along a single axis and thus exhibit a high macroscopic polarization in its solid-state form. Due to the P1 polar packing, the sample can generate second harmonic light efficiently, about three times the intensity of the benchmark potassium dihydrogen phosphate. Our findings show that crystal engineering by hydrogen bonding in a single molecular backbone can be used for controlling the macroscopic NLO properties.

High Active Material Loading in Organic Electrodes Enabled by a Multifunctional Binder.

Organic electrodes are promising candidates for next-generation lithium-ion batteries due to their low cost and sustainable nature; however, they often suffer from very low conductivity and active material loadings. The conventional binder used in organic-based Li-ion batteries is poly(vinylidene fluoride) (PVDF), yet it is electrochemically inactive and thus occupies volume and mass without storing energy. Here, we report an organic mixed ionic-electronic conducting polymer, poly[norbornene-1,2-bis(C(O)OPEDOT)]25-b-[norbornene-1,2-bis-(C(O)PEG12)]25 denoted PEDOT-b-PEG for simplicity, as a cathode binder to address the aforementioned issues. The polymer contains a poly(3,4-ethylenedioxythiophene) (PEDOT) functionality to provide electronic conductivity, as well as poly(ethylene glycol) (PEG) chains to impart ionic conductivity to the cathode composite. We compare electrodes containing a perylene diimide (PDI) active material, conductive carbon, and a polymeric binder (either PVDF or PEDOT-b-PEG) with different weight ratios to study the impact of active material loading and type of binder on the performance of the cell. The lithium-ion cells prepared with the PEDOT-b-PEG polymer binder result in higher capacities and decreased impedance at all active material loadings compared to cathodes prepared with the PVDF-containing electrodes, demonstrating potential as a new binder to achieve higher active material loadings in organic electrodes. The strategy of preparing these polymers should be broadly applicable to other classes of mixed polymer conductors.

Engineering Electro-Optic BaTiO3 Nanocrystals via Efficient Doping.

Electro-optic (EO) modulators provide electrical-to-optical signal conversion relevant to optical communications. Barium titanate (BaTiO3 ) is a promising material system for EO modulation in light of its optical ultrafast nonlinearity, low optical loss, and high refractive index. To enhance further its spontaneous polarization, BaTiO3 can be doped at the Ba and Ti sites; however, doping is often accompanied by ion migration, which diminishes EO performance. Here, donor-acceptor doping and its effect on EO efficiency are investigated, finding that La-doped BaTiO3 achieves an EO coefficient of 42 pm V-1 at 1 kHz, fully twice that of the pristine specimen; however, it is also observed that, with this single-element doping, the EO response falls off rapidly with frequency. From impedance spectroscopy, it is found that frequency-dependent EO is correlated with ion migration. Density functional theory calculations predict that the ion-migration barrier decreases with La3+ doping but can be recovered with further Mn2+ doping, a finding that prompts to prevent ion migration by incorporating Mn2+ into the Ti-site to compensate for the charge imbalance.

Dopant-Stabilized Assembly of Poly(3-hexylthiophene).

Polymer self-assembly is a powerful approach for forming nanostructures for solution-phase applications. However, polymer semiconductor assembly has primarily been driven by solvent interactions. Here, we report poly(3-hexythiophene) homopolymer assembly driven and stabilized by oxidative doping with iron (III) p-toluenesulfonate in benzonitrile. By this improved method, dopant mol % and addition temperature determine the size and morphology of oxidized polymer nanostructures. The dopant counterion provides colloidal stability in a process of dopant-stabilized assembly (DSA). Each variable governing polymer assembly is systematically varied, revealing general principles of oxidized nanostructure assembly and allowing the polymer planarity, optical absorption, and doping level to be modulated. Oxidized nanostructure heights, lengths, and widths are shown to depend on these properties, which we hypothesize is due to competing nanostructure formation and oxidation mechanisms that are governed by the polymer conformation upon doping. Finally, we demonstrate that the nanoparticle oxidative doping level can be tuned post-formation through sequential dopant addition. By revealing the fundamental processes underlying DSA, this work provides a powerful toolkit to control the assembly and optoelectronic properties of oxidatively doped nanostructures in solution.

Homogeneous Synthesis of Monodisperse Sequence-Defined Conjugated Oligomers by Temperature Cycling.

Sequence-defined synthetic oligomers and polymers provide unprecedented opportunities for polymer chemists to finely control properties such as chain folding, self-assembly, and optoelectronic performance of materials. However, absolute control over both chain-length and monomer sequence has been a long-standing "grand challenge" for decades. Herein, we report a novel strategy to synthesize monodisperse sequence-defined conjugated oligomers in a homogeneous manner by temperature cycling, thereby achieving single-monomer precision in conjugated polyheterocycles. A series of sequence-defined oligomers with up to twelve repeating units, four different monomers, and various sequences were successfully synthesized. Monomer sequence was also proved to affect optical properties. We believe this strategy not only exhibits general applicability to the synthesis of group 16 conjugated oligomers and polymers, but also has far-reaching potential for other polymer systems.

Group 16 conjugated polymers based on furan, thiophene, selenophene, and tellurophene.

Five-membered aromatic rings containing Group 16 elements (O, S, Se, and Te), also referred as chalcogenophenes, are ubiquitous building blocks for π-conjugated polymers (CPs). Among these, polythiophenes have been established as a model system to study the interplay between molecular structure, solid-state organization, and electronic performance. The judicious substitution of alternative heteroatoms into polythiophenes is a promising strategy for tuning their properties and improving the performance of derived organic electronic devices, thus leading to the recent abundance of CPs containing furan, selenophene, and tellurophene. In this review, we first discuss the current status of Kumada, Negishi, Murahashi, Suzuki-Miyaura, and direct arylation polymerizations, representing the best routes to access well-defined chalcogenophene-containing homopolymers and copolymers. The self-assembly, optical, solid-state, and electronic properties of these polymers and their influence on device performance are then summarized. In addition, we highlight post-polymerization modifications as effective methods to transform polychalcogenophene backbones or side chains in ways that are unobtainable by direct polymerization. Finally, the major challenges and future outlook in this field are presented.

Synthesis and optoelectronic properties of radical conjugated polyfluorenes.

A novel redox-active fluorene monomer is synthesized and copolymerized with 9,9-dioctylfluorene and benzo[c][1,2,5]thiadiazole via Suzuki cross-coupling to produce alternating and tertiary copolymers. Electrochemical and chemical reduction of the copolymers generates organic polymeric radical anions. Electrochemical, spectroscopic, and photophysical characterization grant insight into the structure-property relationship for open-shell conjugated polymers.

Aqueous zinc batteries: Design principles toward organic cathodes for grid applications.

The development of low-cost and sustainable grid energy storage is urgently needed to accommodate the growing proportion of intermittent renewables in the global energy mix. Aqueous zinc-ion batteries are promising candidates to provide grid storage due to their inherent safety, scalability, and economic viability. Organic cathode materials are especially advantageous for use in zinc-ion batteries as they can be synthesized using scalable processes from inexpensive starting materials and have potential for biodegradation at their end of life. Strategies for designing organic cathode materials for rechargeable zinc-ion batteries targeting grid applications will be discussed in detail. Specifically, we emphasize the importance of cost analysis, synthetic simplicity, end-of-life scenarios, areal loading of active material, and long-term stability to materials design. We highlight the strengths and challenges of present zinc-organic research in the context of our design principles, and provide opportunities and considerations for future electrode design.

Rigid Conjugated Diamine Templates for Stable Dion-Jacobson-Type Two-Dimensional Perovskites.

Hybrid organic-inorganic perovskites (HOIPs) have garnered widespread interest, yet stability remains a critical issue that limits their further application. Compared to their three-dimensional (3D) counterparts, two-dimensional (2D)-HOIPs exhibit improved stability. 2D-HOIPs are also appealing because their structural and optical properties can be tuned according to the choice of organic ligand, with monovalent or divalent ligands forming Ruddlesden-Popper (RP) or Dion-Jacobson (DJ)-type 2D perovskites, respectively. Unlike RP-type 2D perovskites, DJ-type 2D perovskites do not contain a van der Waals gap between the 2D layers, leading to improved stability. However, bifunctional organic ligands currently used to develop DJ-type 2D perovskites are limited to commercially available aliphatic and single-ring aromatic ammonium cations. Large conjugated organic ligands are in demand for their semiconducting properties and their potential to improve materials stability further. In this manuscript, we report the design and synthesis of a new set of larger conjugated diamine ligands and their incorporation into DJ-type 2D perovskites. Compared with analogous RP-type 2D perovskites, DJ 2D perovskites reported here show blue-shifted, narrower emissions and significantly improved stability. By changing the structure of rings (benzene vs thiophene) and substituents, we develop structure-property relationships, finding that fluorine substitution enhances crystallinity. Single-crystal structure analysis and density functional theory calculations indicate that these changes are due to strong electrostatic interactions between the organic templates and inorganic layers as well as the rigid backbone and strong π-π interaction between the organic ligands themselves. These results illustrate that targeted engineering of the diamine ligands can enhance the stability of DJ-type 2D perovskites.

Precision Synthesis of Conjugated Polymers Using the Kumada Methodology.

Since the discovery of conductive poly(acetylene), the study of conjugated polymers has remained an active and interdisciplinary frontier between polymer chemistry, polymer physics, computation, and device engineering. One of the ultimate goals of polymer science is to reliably synthesize structures, similar to small molecule synthesis. Kumada catalyst-transfer polymerization (KCTP) is a powerful tool for synthesizing conjugated polymers with predictable molecular weights, narrow dispersities, specific end groups, and complex backbone architectures. However, expanding the monomer scope beyond the well-studied 3-alkylthiophenes to include electron-deficient and complex heterocycles has been difficult. Revisiting the successful applications of KCTP can help us gain new insight into the CTP mechanisms and thus inspire breakthroughs in the controlled polymerization of challenging π-conjugated monomers.In this Account, we highlight our efforts over the past decade to achieve controlled synthesis of homopolymers (p-type and n-type), copolymers (diblock and statistical), and monodisperse high oligomers. We first give a brief introduction of the mechanism and state-of-the-art of KCTP. Since the extent of polymerization control is determined by steric and electronic effects of both the catalyst and monomer, the polymerization can be optimized by modifying monomer and catalyst structures, as well as finding a well-matched monomer-catalyst system. We discuss the effects of side-chain steric hindrance and halogens in the context of heavy atom substituted monomers. By moving the side-chain branch point one carbon atom away from the heterocycle to alleviate steric crowding and stabilize the catalyst resting state, we were able to successfully control the polymerization of new tellurophene monomers. Inspired by innocent role of the sterically encumbered 2-transmetalated 3-alkylthiophene monomer, we introduce the treatment of hygroscopic monomers with a bulky Grignard compound as a water-scavenger for the improved synthesis of water-soluble conjugated polymers. For challenging electron-deficient monomers, we discuss the design of new Ni(II)diimine catalysts with electron-donating character which enhance the stability of the association complex between the catalyst and the growing polymer chain, resulting in the quasi-living synthesis of n-type polymers. Beyond n-type homopolymers, the Ni(II)diimine catalysts are also capable of producing electron-rich and electron-deficient diblock and statistical copolymers. We discuss how density functional theory (DFT) calculations elucidate the role of catalyst steric and electronic effects in controlling the synthesis of π-conjugated polymers. Moreover, we demonstrate the synthesis of monodisperse high oligomers by temperature cycling, which takes full advantage of the unique character of KCTP in that it proceeds through distinct intermediates that are not reactive. The insight we gained thus far leads to the first example of isolated living conjugated polymer chains prepared by a standard KCTP procedure, with general applicability to different monomers and catalytic systems. In summarizing a decade of innovation in KCTP, we hope this Account will inspire future development in the field to overcome key challenges including the controlled synthesis of electron-deficient heterocycles, complex and high-performance systems, and degradable and recyclable materials as well as cutting-edge catalyst design.

Thiophene- and selenophene-based conjugated polymeric mixed ionic/electronic conductors.

Mixed ionic/electronic conductors (MIECs) are desirable materials for next-generation electronic devices and energy storage applications. Polymeric MIECs are attractive from the standpoint that their structure can be controlled and anticipated to have mechanically robust properties. Here, we prepare and investigate conjugated copolymers containing thiophene and selenophene repeat units and their homopolymer counterparts. Specifically, thiophene bearing a triethylene glycol (EG3) side chain was polymerized and copolymerized with dodecyl thiophene/selenophene monomers. The synthesis leads to a class of copolymers that contain either S or Se and are blocky in nature. The Li-ion conductivity of ionically doped copolymers, P3DDT-s-P3(EG3)T and P3DDS-s-P3(EG3)T (9.7 × 10-6 and 8.2 × 10-6 S/cm, respectively), was 3-4 fold higher than that of the ionically doped constituent homopolymer, P3(EG3)T (2.2 × 10-6 S/cm), at ambient conditions. The electronic conductivity of the oxidatively doped copolymers was significantly higher than that of the constituent homopolymer P3(EG3)T, and most notably, P3DDS-s-P3(EG3)T reached ∼7 S/cm, which is the same order of magnitude as poly(3-dodecylthiophene) and poly(3-dodecylselenophene), which are the highest oxidatively doped conductors based on control experiments. Our findings provide implications for designing new MIECs based on copolymerization and the incorporation of heavy atom heterocycles.

Polyacetylene Revisited: A Computational Study of the Molecular Engineering of N-type Polyacetylene.

The development of stable and highly conductive polymers, particularly n-type materials, remains an outstanding challenge in organic electronics. N-doped polyacetylene has long been studied as a highly conductive organic n-type material but suffers from extremely poor stability. Herein, we use DFT to model a series of n-doped polyacetylene derivatives, which have been functionalized with a range of electron-withdrawing substituents, with the goal of identifying attractive candidates for synthesis. We analyze the predicted molecular orbital energies, polymer planarity, and delocalization of charge carriers along the polymer backbone. In so doing, we develop key insights about the ideal substituents for both stable and highly conductive polyacetylene derivatives. This work will inform the modern synthesis and development of new polyacetylene derivatives. Beyond this, the work identifies a variety of new materials that have not yet been synthesized and should be good candidates for emerging optoelectronic applications including soft thermoelectrics, bioelectronics, and flexible device technologies.

Programmable Assembly of π-Conjugated Polymers.

π-Conjugated polymers have numerous applications due to their advantageous optoelectronic and mechanical properties. These properties depend intrinsically on polymer ordering, including crystallinity, orientation, morphology, domain size, and π-π interactions. Programming, or deliberately controlling the composition and ordering of π-conjugated polymers by well-defined inputs, is a key facet in the development of organic electronics. Here, π-conjugated programming is described at each stage of material development, stressing the links between each programming mode. Covalent programming is performed during polymer synthesis such that complex architectures can be constructed, which direct polymer assembly by governing polymer orientation, π-π interactions, and morphological length-scales. Solution programming is performed in a solvated state as polymers dissolve, aggregate, crystallize, or react in solution. Solid-state programming occurs in the solid state and is governed by polymer crystallization, domain segregation, or gelation. Recent progress in programming across these stages is examined, highlighting order-dependent features and assembly techniques that are unique to π-conjugated polymers. This should serve as a guide for delineating the many ways of directing π-conjugated polymer assembly to control ordering, structure, and function, enabling the further development of organic electronics.

Robust Electrodes for Flexible Energy Storage Devices Based on Bimetallic Encapsulated Core-Multishell Structures.

Developing flexible electrodes with high active materials loading and excellent mechanical stability is of importance to flexible electronics, yet remains challenging. Herein, robust flexible electrodes with an encapsulated core-multishell structure are developed via a spraying-hydrothermal process. The multilayer electrode possesses an architecture of substrate/reduced graphene oxide (rGO)/bimetallic complex/rGO/bimetallic complex/rGO from the inside to the outside, where the cellulosic fibers serve as the substrate, namely, the core; and the multiple layers of rGO and bimetallic complex, are used as active materials, namely, the shells. The inner two rGO interlayers function as the cement that chemically bind to two adjacent layers, while the two outer rGO layers encapsulate the inside structure effectively protecting the electrode from materials detachment or electrolyte corrosion. The electrodes with a unique core-multishell structure exhibit excellent cycle stability and exceptional temperature tolerance (-25 to 40 °C) for lithium and sodium storage. A combination of experimental and theoretical investigations are carried out to gain insights into the synergetic effects of cobalt-molybdenum-sulfide (CMS) materials (the bimetallic complex), which will provide guidance for future exploration of bimetallic sulfides. This strategy is further demonstrated in other substrates, showing general applicability and great potential in the development of flexible energy storage devices.

Trends in Conjugated Chalcogenophenes: A Theoretical Study.

Heavy atom substitution in chalcogenophenes is a versatile strategy for tailoring and ultimately improving conjugated polymer properties. While thiophene monomers are commonly implemented in polymer designs, relatively little is known regarding the molecular properties of the heavier chalcogenophenes. Herein, we use density functional theory (DFT) calculations to examine how group 16 heteroatoms, including the radioactive polonium, affect polychalcogenophene properties including bond length, chain twisting, aromaticity, and optical properties. Heavier chalcogenophenes are more quinoidal in character and consequently have reduced band gaps and larger degrees of planarity. We consider both the neutral and radical cationic species. Upon p-type doping, bond length rearrangement is indicative of a more delocalized electronic structure, which combined with optical calculations is consistent with the polaron-model of charge storage on conjugated polymer chains. A better understanding of the properties of these materials at their molecular levels will inevitably be useful in material design as the polymer community continues to explore more main group containing polymers to tackle issues in electronic devices.