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At least 73 records · Page 4

Dual-Emitting Cyclometalated Platinum Compounds with Isocyanide Ligands

Cyclometalated platinum(II) compounds with both C^N chelating iminic ligands and isocyanide ligands were synthesized. Two sets of compounds from the reaction of two separate HC^N ligands (derived from thiophene or benzene) with [Pt2Me4(μ-SMe 2 ) 2 ] were obtained, resulting in square planar compounds with an anionic C^N ligand, a methyl ligand, and a dimethyl sulfide (dms) ligand completing the coordination sphere. Subsequently, the dms ligand was easily substituted by several isocyanide ligands (2-naphthyl, adamantyl, 2,6-dimethylphenyl, ptoluenesulfonylmethyl). The compounds were characterized by multinuclear NMR spectroscopy, IR spectroscopy, and singlecrystal X-ray diffraction (SCXRD). Their photophysical properties were explored using UV/vis, emission, and transient absorption (TA) spectroscopy. The emission spectra for the thiophene-derived compounds showed well-defined dual emission peaks, while the benzene-derived compounds’ bands appeared less resolved. DFT and TDDFT calculations were performed, and results were compared to the observed spectroscopic properties of the newly synthesized complexes.

Inorganic carbon compounds↗

Discovery of tunable and soluble organic emitters for solid-state lasers with a self-driving laboratory

We have recently demonstrated the ability of using self-driving laboratories for AI-driven searches of organic emitters for solid-state lasing devices. Our past workflow featured solubility challenges for such large molecular moieties. In this next-generation study, we return to the drawing board to explore a family of com-pounds that are much solution processable and composed of a set of electronic cores that provide a broader color response. Out of 252 potential candidates,and with guidance from DFT calculations, we selectively perform a compre-hensive study exploring 51 fluorene-based A-B-A type organic laser oligomers, armed with our self-driving lab. The candidates range from simple hydrocarbon molecules to complex hetero atom-mixed molecules. As a result of this study, we highlight diketopyrrolopyrrole and benzodiazole derivatives for their largely red-shifted emissions. Furthermore, we investigate the effect of color change aris-ing from hetero atom permutation, fluorine addition, thiophene coupling, and a combination of fluorine addition and thiophene coupling. Amplified spontaneous emission (ASE) measurements in the solid state further corroborate the lasing potential of selected candidates, reinforcing their suitability for future device applications. The computational study with density functional theory confirms the experimental results.

fluorescence↗

Highly stretchable organic electrochemical transistors with strain-resistant performance

Realizing fully stretchable electronic materials is central to advancing new types of mechanically agile and skin-integrable optoelectronic device technologies. Here we demonstrate a materials design concept combining an organic semiconductor film with a honeycomb porous structure with biaxially prestretched platform that enables high-performance organic electrochemical transistors with a charge transport stability over 30-140% tensional strain, limited only by metal contact fatigue. In this work, the prestretched honeycomb semiconductor channel of donor-acceptor polymer poly(2,5-bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)-2,5-diketo-pyrrolopyrrole-alt-2,5-bis(3-triethyleneglycoloxy-thiophen-2-yl) exhibits high ion uptake and completely stable electrochemical and mechanical properties over 1,500 redox cycles with 10(4) stretching cycles under 30% strain. Invariant electrocardiogram recording cycles and synapse responses under varying strains, along with mechanical finite element analysis, underscore that the present stretchable organic electrochemical transistor design strategy is suitable for diverse applications requiring stable signal output under deformation with low power dissipation and mechanical robustness. Highly stretchable organic electrochemical transistors with stable charge transport under severe tensional strains are demonstrated using a honeycomb semiconducting polymer morphology, thereby enabling controllable signal output for diverse stretchable bioelectronic applications.

36 MATERIALS SCIENCE↗

Side chain engineering control of mixed conduction in oligoethylene glycol-substituted polythiophenes

A major limitation for polymeric mixed ionic/electronic conductors (MIECs) is the trade-off between ionic and electronic conductivity; changes made that improve one typically hinder the other. In order to address this fundamental problem, this work provides insight into ways that we could improve one type of conduction without hindering the other. Here, we investigated a common oligoethylene glycol side chain polymer by adjusting the oxygen atom content and position, providing structural insights for materials that better balanced the two conduction pathways. The investigated polymer series showed the prototypical conflict between ionic and electronic conduction for oxygen atom content, with increasing oxygen atom content increasing ionic conductivity, but decreasing electronic conductivity; however, by increasing the oxygen atom distance from the polymer backbone, both ionic and electronic conductivity could be improved. Following these rules, we show that poly(3-(methoxyethoxybutyl)thiophene), when blended with lithium bistrifluoromethanesulfonimide (LiTFSI), matches the ionic conductivity of a comparable MIEC [poly(3-(methoxyethoxyethoxymethyl)thiophene)], while simultaneously showing higher electronic conductivity, highlighting the potential of this design strategy. We also provide strategies for tuning the MIEC performance to fit a desired application, depending on if electronic, ionic, or balanced conduction is most important. These results have implications beyond just polythiophene-based MIECs, as these strategies for balancing backbone crystallization and coordinating group interconnectivity apply for all semicrystalline conjugated polymers.

36 MATERIALS SCIENCE↗

Aqueous processing of organic semiconductors enabled by stable nanoparticles with built-in surfactants

The introduction of oligoether side chains onto a polymer backbone can help to stabilise polymeric dispersions in water without the necessity of surfactants or additives when conjugated polymer nanoparticles are prepared. A series of poly(3-hexylthiophene) (P3HT) derivatives with different content of a polar thiophene derivative 3-((2-methoxyethoxy)methyl)thiophene was interrogated to find the effect of the polar chains on the stability of the formed nanoparticles, as well as their structural, optical, electrochemical, and electrical properties. Findings indicated that incorporation of 10–20 percent of the polar side chain led to particles that are stable over a period of 42 days, with constant particle size and polydispersity, however the particles from the polymer with 30 percent polar side chain showed aggregation effects. The polymer dispersions showed a stronger solid-like behaviour in water with decreasing polar side chain content, while thin film deposition from water was found to afford globular morphologies and crystallites with more isotropic orientation compared to conventional solution-processed films. As a proof-of-principle, field-effect transistors were fabricated directly from the aqueous dispersions demonstrating that polymers with hydrophilic moieties can be processed in water without the requirement of surfactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reaction dynamics of S( 3 P) with 1,3-butadiene and isoprene: crossed-beam scattering, low-temperature flow experiments, and high-level electronic structure calculations

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S( 3 P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H 2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C 3 H 4 S (loss of ethene or H 2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles.

Lang, Jinxin↗

Microstructure and heteroatom dictate the doping mechanism and thermoelectric properties of poly(alkyl-chalcogenophenes)

Heteroatom substitution can favorably alter electronic transport in conductive polymers to improve their thermoelectric performance. Here we report the spectroscopic, structural, and thermoelectric properties of poly(3–(3',7'-dimethyloctyl) chalcogenophenes) or P3RX doped with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), where the heteroatom [X = thiophene (T), selenophene (Se), tellurophene (Te)], the doping methodology, and extent of doping are systematically varied. Spectroscopic measurements reveal that while all P3RX polymers are appreciably doped, the doping mechanism is inherently different. Poly(3-hexylthiophene) (P3HT, used as a control) and poly(3–(3',7'-dimethyloctyl)tellurophene) (P3RTe) are doped primarily via integer charge transfer (ICT), whereas poly(3–(3',7'-dimethyloctyl)selenophene) (P3RSe) and poly(3–(3',7'-dimethyloctyl)thiophene) (P3RT) are doped via charge transfer complex (CTC) mechanisms. Despite these differences, all polymers saturate with roughly the same number of F4TCNQ counterions (1 dopant per 4 to 6 heterocycles), reinforcing the idea that the extent of charge transfer varies with the doping mechanism. Grazing incidence wide-angle x-ray scattering measurements provide insight into the structural driving forces behind different doping mechanisms—P3RT and P3RSe have similar microstructures in which F4TCNQ intercalates between the π-stacked backbones resulting in CTC doping (localized carriers), while P3HT and P3RTe have microstructures in which F4TCNQ intercalates in the alkyl side chain region, giving rise to ICT doping (delocalized carriers). These structural and spectroscopic observations shed light on why P3HT and P3RTe obtain electrical conductivities ca. 3 S/cm, while P3RT and P3RSe have conductivities <10–3 S/cm under the same thin film processing conditions. Ultimately, this work quantifies the effects of heteroatom, microstructural ordering, extent of doping, and doping mechanism, thereby providing rational guidance for designing future thermoelectric polymer-dopant systems.

36 MATERIALS SCIENCE↗

Co-Design of Charge Transport Superhighways to Connect Catalytic Sites in Soft Photoelectrochemical Systems

Efficient photon-to-electron-to-molecule conversion requires multi-length scale control over charge transport pathways, where electronic charges are delivered to catalytic sites under high mass transport flux. A fundamental question is how can we co-design charge transport pathways to promote efficient charge transfer to/from catalytic sites in complex three-dimensional architectures? Soft conducting polymer systems offer exceptional promise to provide three-dimensional charge transport networks, where electrolyte (ion and solvent) can interdiffuse to promote long-lived charge carriers and the molecular nature allows for strategic synthetic design of catalytic sites. Herein we combine theoretical and experimental approaches to investigate the earliest stages of photoelectrochemical deposition of near-surface catalytic sites (Pt) on soft bulk heterojunction polymeric semiconductors composed of a prototype donor (PTB7-Th) and a prototype acceptor (N2200) as a model system towards better understanding molecular catalyst-polymer site interactions. We focus initially on photoelectrochemical deposition of low Pt loadings, nanoparticle sizes (formed by progressive nucleation) below 20 nm, for both density functional theory (DFT) modeling studies and for spectroscopic characterization using surface-sensitive X-ray and UV-photoemission (XPS/UPS). DFT modeling of “n-type” N2200 slabs reveal for the first time that sulfur atoms in the thiophene units serve as the lowest-energy adsorption sites for single Pt atoms, while larger Pt clusters engage more complexly with both thiophene and naphthalene diimide (NDI) core sites. Changes in chemical composition observed by X-ray photoelectron spectroscopy (XPS) support the DFT predictions, and the angle-resolved measurements reveal that Pt nucleation initiates at subsurface sites which appear to be localized active domains that promote charge transport/transfer and enable vertical growth toward the surface. These results suggest that light-activated Pt nanoparticle deposition decorates energetically distinct sites, where photoactivity is dictated by the local energetics of those sites, and the fact that they represent the termini of charge transport “super-highways” – a small percentage of the total volume of the donor/acceptor polymeric active layer which carries most of the photocurrent generated during both Pt deposition and photoelectrochemical HER. We posit that these initial studies provide a foundational strategy for design of catalytic sites in the near surface regions of complex polymeric materials and advancing soft semiconductor-based photoelectrochemical systems. Achieving a nanometer-scale understanding of catalyst deposition and the impact of local composition and energetics on that placement, should ultimately provide the design guidelines (co-design) for a broad array of catalysts at sites that optimize that efficiency and maximize platform durability.

14 SOLAR ENERGY↗

Introducing Low-Cost Pyrazine Unit into Terpolymer Enables High-Performance Polymer Solar Cells with Efficiency of 18.23%

Recently, a random ternary copolymerization strategy has become a promising and efficient approach to develop high-performance polymer donors for polymer solar cells (PSCs). Here, in this study, a low-cost electron-withdrawing unit, 2,5-bis(4-(2-ethylhexyl)thiophen-2-yl)pyrazine (PZ-T), is incorporated into the polymer backbone of PM6 as the third component, and three D-A 1 -D-A 2 type terpolymers PMZ-10, PMZ-20, and PMZ-30 are synthesized by the random copolymerization strategy, with the PZ-T proportion of 10%, 20%, and 30%, respectively. The terpolymers exhibit downshifted highest occupied molecular orbital energy levels than PM6, which is beneficial for obtaining higher open-circuit voltage (V oc ) of the PSCs with the polymer as a donor. Importantly, the PSCs based on PMZ-10:Y6 demonstrate efficient exciton dissociation, higher and balanced electron/hole mobilities, desirable aggregation, and high power conversion efficiency of 18.23%, which is the highest efficiency among the terpolymer-based PSCs so far. The results indicate that the ternary copolymerization strategy with PZ-T as the second A-unit is an efficient approach to further improve the photovoltaic performance and reduce the synthetic cost of the D-A copolymer donors.

36 MATERIALS SCIENCE↗

Stable High‐Conductivity Ethylenedioxythiophene Polymers via Borane‐Adduct Doping

Efficient doping of polymer semiconductors is required for high conductivity and efficient thermoelectric performance. Lewis acids, e.g., B(C 6 F 5 ) 3 , have been widely employed as dopants, but the mechanism is not fully understood. 1:1 “Wheland type” or zwitterionic complexes of B(C 6 F 5 ) 3 are created with small conjugated molecules 3,6-bis(5-(7-(5-methylthiophen-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)thiophen-2-yl)-2,5-dioctyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione [oligo_DPP(EDOT) 2 ] and 3,6-bis(5''-methyl-[2,2':5',2''-terthiophen]-5-yl)-2,5-dioctyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione [oligo_DPP(Th) 2 ]. Using a wide variety of experimental and computational approaches, the doping ability of these Wheland Complexes with B(C 6 F 5 ) 3 are characterized for five novel diketopyrrolopyrrole-ethylenedioxythiophene (DPP-EDOT)-based conjugated polymers. The electrical properties are a strong function of the specific conjugated molecule constituting the adduct, rather than acidic protons generated via hydrolysis of B(C 6 F 5 ) 3 , serving as the oxidant. It is highly probable that certain repeat units/segments form adduct structures in p -type conjugated polymers which act as intermediates for conjugated polymer doping. Electronic and optical properties are consistent with the increase in hole-donating ability of polymers with their cumulative donor strengths. The doped film of polymer (DPP(EDOT) 2 -(EDOT) 2 ) exhibits exceptionally good thermal and air-storage stability. The highest conductivities, ≈300 and ≈200 S cm -1 , are achieved for DPP(EDOT) 2 -(EDOT) 2 doped with B(C 6 F 5 ) 3 and its Wheland complexes.

36 MATERIALS SCIENCE↗

Coherent Phonon-Induced Modulation of Charge Transfer in 2D Hybrid Perovskites

Electron–phonon interactions play an essential role in charge transport and transfer processes in semiconductors. For most structures, tailoring electron–phonon interactions for specific functionality remains elusive. Here, it is shown that, in hybrid perovskites, coherent phonon modes can be used to manipulate charge transfer. In the 2D double perovskite, (AE2T) 2 AgBiI 8 (AE2T: 5,5“-diylbis(amino-ethyl)-(2,2”-(2)thiophene)), the valence band maximum derived from the [Ag 0.5 Bi 0.5 I4] 2– framework lies in close proximity to the AE2T-derived HOMO level, thereby forming a type-II heterostructure. During transient absorption spectroscopy, pulsed excitation creates sustained coherent phonon modes, which periodically modulate the associated electronic levels. Thus, the energy offset at the organic–inorganic interface also oscillates periodically, providing a unique opportunity for modulation of interfacial charge transfer. Density-functional theory corroborates the mechanism and identifies specific phonon modes as likely drivers of the coherent charge transfer. These observations are a striking example of how electron–phonon interactions can be used to manipulate fundamentally important charge and energy transfer processes in hybrid perovskites.

36 MATERIALS SCIENCE↗

Double Doping of Semiconducting Polymers Using Ion-Exchange with a Dianion

The interactions between counterions and electronic carriers in electrically doped semiconducting polymers are important for delocalization of charge carriers, electronic conductivity, and thermal stability. The introduction of a dianions in semiconducting polymers leads to double doping where there is one counterion for two charge carriers. Double doping minimizes structural distortions, but changes the electrostatic interactions between the carriers and counterions. Polymeric ionic liquids (PIL) with croconate dianions are helpful to investigate the role of the counterion in p-type semiconducting polymers. PILs prevent diffusion of the cation into the semiconducting polymers during ion exchange. The redox-active croconate dianions undergo ion exchange with doped semiconducting polymers depending on their ionization energy. Croconate dianions are found to reduce doped films of poly(3-hexyl thiophene), but undergo ion exchange with a polythiophene with tetraethylene glycol side chains, P(g 4 2T-T), that has a lower ionization energy. The croconate dianion maintains crystalline order in P(g 4 2T-T) and leads to a lower activation energy for the electrical conductivity than PF 6 – counterions. The control of the doping level with croconate allows optimization of the thermoelectric performance of the semiconducting polymer. Finally, the thermal stability of the doped films of P(g 4 2T-T) is found to depend strongly on the nature of the counterion.

36 MATERIALS SCIENCE↗

On the Importance of Chemical Precision in Organic Electronics: Fullerene Intercalation in Perfectly Alternating Conjugated Polymers

Abstract The true structure of alternating conjugated polymers—the state‐of‐the‐art materials for many organic electronics—often deviates from the idealized picture. Homocoupling defects are in fact inherent to the widely used cross‐coupling polymerization methods. Nevertheless, many polymers still perform excellently in the envisaged applications, which raises the question if one should really care about these imperfections. This article looks at the relevance of chemical precision (and lack thereof) in conjugated polymers covering the entire spectrum from the molecular scale, to the micro and mesostructure, up to the device level. The different types of polymerization errors for the alkoxylated variant of the benchmark (semi)crystalline polymer poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐ b ]thiophene (PBTTT) are identified, visualized, and quantified and a general strategy to avoid homocoupling is introduced. Through a combination of experiments and supported by simulations, it is shown that these coupling defects hinder fullerene intercalation and limit device performance as compared to the homocoupling‐free analog. This clearly demonstrates that structural defects do matter and should be generally avoided, in particular when the geometrical regularity of the polymer is essential. These insights likely go beyond the specific PBTTT derivatives studied here and are of general relevance for the wider organic electronics field.

36 MATERIALS SCIENCE↗

Solution–Doped Donor–Acceptor Copolymers Based on Diketopyrrolopyrrole and 3, 3'–Bis (2–(2–(2–Methoxyethoxy) Ethoxy) ethoxy)–2, 2'–Bithiophene Exhibiting Outstanding Thermoelectric Power Factors with p –Dopants

The design of polymeric semiconductors exhibiting high electrical conductivity (σ) and thermoelectric power factor (PF) will be vital for flexible large-area electronics. In this work, four polymers based on diketopyrrolopyrrole (DPP), 2,3-dihydrothieno[3,4-b][1,4]dioxine (EDOT), thieno[3,2-b]thiophene (TT), and 3, 3'-bis (2-(2-(2-methoxyethoxy) ethoxy) ethoxy)-2, 2'-bithiophene (MEET) are investigated as side-chains, with the MEET polymers newly synthesized for this study. These polymers are systematically doped with tetrafluorotetracyanoquinodimethane ( F 4 TCNQ), CF3SO3H, and the synthesized dopant Cp(CN) 3 -(COOMe) 3 , differing in geometry and electron affinity. The DPP-EDOT-based polymer containing MEET as side-chains exhibits the highest conductivity (σ) ≈700 S cm–1 in this series with the acidic dopant (CF 3 SO 3 H). This polymer also shows the lowest oxidation potential by cyclic voltammetry (CV), the strongest intermolecular interactions evidenced by differential scanning calorimetry (DSC), and has the most oxygen-based functionality for possible hydrogen bonding and ionic screening. Other polymers exhibit high σ ≈300–500 S cm–1 and power factor up to 300 µW m –1 K –2 . The mechanism of conductivity is predominantly electronic, as validated by time-dependent conductance studies and transient thermo voltage monitoring over time, including for those doped with the acid. Furthermore, these materials maintain significant thermal stability and air stability over ≈6 weeks. Density functional theory calculations reveal molecular geometries and inform about frontier energy levels. Raman spectroscopy, in conjunction with scanning electron microscopy (SEM-EDS) and x-ray diffraction, provides insight into the solid-state microstructure and degree of phase separation of the doped polymer films. Infrared spectroscopy enables this study to further quantify the degree of charge transfer from polymer to dopant.

36 MATERIALS SCIENCE↗

Design Principles of Diketopyrrolopyrrole‐Thienopyrrolodione Acceptor 1 –Acceptor 2 Copolymers

Abstract The design principles of acceptor 1 –acceptor 2 copolymers featuring alternating diketopyrrolopyrrole (DPP) and thienopyrrolodione (TPD) moieties are investigated. The investigated series of polymers is obtained by varying the aromatic linker between the two acceptor motifs between thiophene, thiazole, pyridine, and benzene. High electron affinities between 3.96 and 4.42 eV, facilitated by the synergy of the acceptor motifs are determined with optical gaps between 1.37 and 2.02 eV. Grazing incidence wide‐angle X‐ray scattering studies reveal a range of film morphologies after thermal annealing, including face‐on, end‐on and superstructure edge‐on‐like crystallites. Conversely, all materials form thin edge‐on layers on the polymer–air interface, as demonstrated by multi‐elemental near‐edge X‐ray absorption fine‐structure spectroscopy. The benefit of the electron‐deficient linkers thiazole and pyridine is evident: In organic field effect transistors, electron mobilities of up to 4.6 × 10 −2 cm 2 V −1 s −1 are obtained with outstanding on/off current ratios of 5 × 10 5 , facilitated by the absence of detectable hole transport in these materials. Viability for all‐polymer solar cells is assessed in active layer blends with the donor polymer PM6, yielding a maximum average power conversion efficiency of 4.8% and an open circuit voltage above 1 V.

36 MATERIALS SCIENCE↗

Photoluminescence Probes Ion Insertion into Amorphous and Crystalline Regions of Organic Mixed Conductors

Abstract Organic mixed ionic‐electronic conductors (OMIECs) have emerged as promising materials for a wide range of next‐generation technologies, including bioelectronics and neuromorphic computing. The performance of these materials depends on the transport of ions through the polycrystalline polymer matrix as well as how the distribution of ions and polarons in crystalline and amorphous regions impacts electronic transport. However, it is often challenging to distinguish whether ions enter crystalline or amorphous regions. In this work, steady‐state and time‐resolved photoluminescence (PL) spectroelectrochemistry is used to probe initial ion insertion in crystalline and amorphous regions of the OMIEC material poly(3‐[2‐[2‐(2‐methoxyethoxy)ethoxy]ethyl]thiophene ‐2,5‐diyl) (P3MEEET) as a function of applied voltage. It is found that PL spectroelectrochemistry reports on the initial stages of electrochemical doping through the quenching of PL emission. By distinguishing between amorphous and crystalline contributions to the PL spectrum, ion insertion in crystalline and amorphous regions as a function of voltage is tracked. It is found that PL spectroelectrochemistry is much more sensitive to the initial injection of ions than complementary methods, highlighting its potential as a sensitive tool for interrogating ion injection in OMIECs.

Collins, Garrett W.↗