Search

Interest in high-spin organic materials is driven by opportunities to enable far-reaching fundamental science and develop technologies that integrate light element spin, magnetic, and quantum functionalities. Although extensively studied, the intrinsic instability of these materials complicates synthesis and precludes an understanding of how fundamental properties associated with the nature of the chemical bond and electron pairing in organic materials systems manifest in practical applications. Here, we demonstrate a conjugated polymer semiconductor, based on alternating cyclopentadithiophene and thiadiazoloquinoxaline units, that is a ground-state triplet in its neutral form. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-to-low spin energy gap of 9.30 × 10-3 kcal mol-1. The strongly correlated electronic structure, very narrow bandgap, intramolecular ferromagnetic coupling, high electrical conductivity, solution processability, and robust stability open access to a broad variety of technologically relevant applications once thought of as beyond the current scope of organic semiconductors.

Organic semiconducting donor–acceptor polymers are promising candidates for stretchable electronics owing to their mechanical compliance. However, the effect of the electron-donating thiophene group on the thermomechanical properties of conjugated polymers has not been carefully studied. Here, thin-film mechanical properties are investigated for diketopyrrolopyrrole (DPP)-based conjugated polymers with varying numbers of isolated thiophene moieties and sizes of fused thiophene rings in the polymer backbone. Interestingly, it is found that these thiophene units act as an antiplasticizer, where more isolated thiophene rings or bigger fused rings result in an increased glass transition temperature (T g ) of the polymer backbone, and consequently elastic modulus of the respective DPP polymers. Detailed morphological studies suggests that all samples show similar semicrystalline morphology. This antiplasticization effect also exists in para-azaquinodimethane-based conjugated polymers, indicating that this can be a general trend for various conjugated polymer systems. Using the knowledge gained above, a new DPP-based polymer with increased alkyl side chain density through attaching alky chains to the thiophene unit is engineered. The new DPP polymer demonstrates a record low T g , and 50% lower elastic modulus than a reference polymer without side-chain decorated on the thiophene unit. This work provides a general design rule for making low-T g conjugated polymers for stretchable electronics.

Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub-picosecond singlet exciton lifetimes are measured in a structurally related series of infrared-absorbing copolymers that consist of alternating cyclopentadithiophene electron-rich “push” units and strong electron-deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC71BM infrared photodetectors is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single-chain excitons unquenched. The results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed.

Donor-acceptor (DA) conjugated polymers provide an important platform for the development of solution-processed optoelectronic devices. The complex interrelation between electronic properties and conformational disorder in these materials complicates the identification of design guidelines to control the bandgap at low energies, limiting the design of new optoelectronic and device functionalities. Here, we demonstrate that DA polymers comprised of exocyclic olefin substituted cyclopentadithiophene donors, in combination with conventional electron acceptors, display very narrow optical bandgaps (1.2 > Eoptg > 0.7 eV) and primary photoexcitations extending into the shortwave infrared. Theoretical calculations reveal fundamental structure-property relationships toward bandgap and energy level control in these spectral regions. Bulk heterojunction photodiodes fabricated using these new materials demonstrate a detectivity (D∗) of > 1011 Jones within a spectral range of 0.6-1.43 μm and measurable D∗ to 1.8 μm, the longest reported to date for conjugated polymer based systems.

Narrow band gap donor-acceptor conjugated polymers present excellent paradigms in photonics and optoelectronics due to their chemical tunability, correlated electronic structures, and tunable open-shell electronic configurations. However, rational design for enhancing the properties of these molecular systems remains challenging. In this study, we employed density functional theory (DFT) calculations to investigate prototypical narrow band gap donor-acceptor conjugated oligomers, consisting of alternating cyclopentadithiophene (CPDT) donors paired with benzothiadiazole (BT), benzoselenadiazole (BSe), benzobisthiadiazole (BBT), and thiadiazoloquinoxaline (TQ) acceptors. Analyses of structures, singlet-triplet gaps, and absorption spectra of oligomers with up to ten repeat units have shown that when incorporating the BT, BSe, and TQ acceptors, the backbone curvature resulted in spiral structures that were energetically favored over their linear counterparts, causing differences in the calculated circular dichroism spectra. Oligomers with BBT-based acceptors preferred, however, a linear geometry, consistent with an open-shell electronic structure. Calculated singlet-triplet splittings demonstrated the importance of long chains and specific structures for consistency with the experiment, while effects of the solvent were also quantified. Based on the predicted low-energy conformations, one-photon absorption spectra for the considered oligomers have shown that using the Tamm-Dancoff approximation within time-dependent DFT for the large systems offers good agreement with the first absorption maxima in measured experimental spectra, thus validating the method for large donor-acceptor oligomers. Natural transition orbital analyses provided insights into the excited-state characteristics. Two-photon absorption maxima were accurately predicted, but the cross-sections were overestimated or underestimated, as dependent on the level of theory employed, to be addressed in future work.

Open-shell conjugated polymers (CPs) offer new opportunities for the development of emerging technologies that utilize the spin degree of freedom. Their light-element composition, weak spin-orbit coupling, synthetic modularity, high chemical stability, and solution-processability offer attributes that are unavailable from other semiconducting materials. However, developing an understanding of how electronic structure correlates with emerging transport phenomena remains central to their application. Here, the first connections between molecular, electronic, and solid-state transport in a high-spin donor-acceptor CP, poly(4-(4-(3,5-didodecylbenzylidene)-4H-cyclopenta[2,1-b:3,4-b']dithiophen-2-yl)-6,7-dimethyl-[1,2,5]-thiadiazolo[3,4-g]quinoxaline), are provided. At low temperatures (T < 180 K), a giant negative magnetoresistance (MR) is achieved in a thin-film device with a value of -98% at 10 K, which surpasses the performance of all other organic materials. The thermal depopulation of the high-spin manifold and negative MR decrease as temperature increases and at T > 180 K, the MR becomes positive with a relatively large MR of 13.5% at room temperature. Variable temperature electron paramagnetic resonance spectroscopy and magnetic susceptibility measurements demonstrate that modulation of both the sign and magnitude of the MR correlates with the electronic and spin structure of the CP. These results indicate that donor-acceptor CPs with open-shell and high-spin ground states offer new opportunities for emerging spin-based applications., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Photodetectors operating across the short-, mid-, and long-wave infrared (SWIR-LWIR, λ = 1-14 µm) underpin modern science, technology, and society in profound ways. Narrow bandgap semiconductors that form the basis for these devices require complex manufacturing, high costs, cooling, and lack compatibility with silicon electronics, attributes that remain prohibitive for their widespread usage and the development of emerging technologies. Here, a photoconductive detector, fabricated using a solution-processed narrow bandgap conjugated polymer is demonstrated that enables charge carrier generation in the infrared and ultrasensitive SWIR-LWIR photodetection at room temperature. Devices demonstrate an ultralow electronic noise that enables outstanding performance from a simple, monolithic device enabling a high detectivity (D*, the figure of merit for detector sensitivity) >2.44 × 10 9 Jones (cm Hz 1/2  W -1 ) using the ultralow flux of a blackbody that mirrors the background emission of objects. These attributes, ease of fabrication, low dark current characteristics, and highly sensitive operation overcome major limitations inherent within modern narrow-bandgap semiconductors, demonstrate practical utility, and suggest that uncooled detectivities superior to many inorganic devices can be achieved at high operating temperatures., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Organic retinomorphic sensors offer the advantage of in-sensor processing to filter out redundant static backgrounds and are well suited for motion detection. To improve this promising structure, here, the key role of interfacial energetics in promoting charge accumulation to raise the inherent photoresponse of the light-sensitive capacitor is studied. Specifically, incorporating appropriate interfacial layers around the photoactive layer is crucial to extend the carrier lifetime, as confirmed by intensity-modulated photovoltage spectroscopy. Compared to its photodiode counterpart, the retinomorphic sensor shows better detectivity and response speed due to the additional insulating layer, which reduces the dark current and the RC time constant. Lastly, three retinomorphic sensors are integrated into a line array to demonstrate the detection of movement speed and direction, showing the potential of retinomorphic designs for efficient motion tracking., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Shortwave infrared (SWIR, λ = 1-3 µm) photodetectors typically use compound semiconductors that are fabricated using high-temperature epitaxial growth and require active cooling. New technologies that overcome these constraints are the focus of intensive current research. Herein, oxidative chemical vapor deposition (oCVD) is used for the first time to create a room temperature, vapor-phase deposited SWIR photoconductive detector with a unique tangled wire film morphology that detects nW-level photons emitted from a 500 °C cavity blackbody radiator-a rarity for polymer systems. A new, window-based process that greatly simplifies device fabrication is used to construct doped polythiophene-based SWIR sensors. The detectors feature an 8.97 kΩ dark resistance and are limited by 1/f noise. They feature an external quantum efficiency (gain-external quantum efficiency) product of 395% and have a measured specific detectivity (D*) of 10 6 Jones, with the potential to reach D* = 10 10 Jones after 1/f noise is minimized. Still, the measured D* is only a factor of 10 2 lower than a typical microbolometer and after optimization, the newly described oCVD polymer-based IR detectors will be in a category competitive with commercially available, room temperature lead salt photoconductors and within reach of room temperature photodiodes., (© 2023 Wiley-VCH GmbH.)

Structural supercapacitors hold promise to expand the energy capacity of a system by integrating load-bearing and energy-storage functions in a multifunctional structure, resulting in weight savings and safety improvements. Here, we develop strategies based on interfacial engineering to advance multifunctional efficiency. The structural electrodes were reinforced by coating carbon-fiber weaves with a uniquely stable conjugated redox polymer and reduced graphene oxide that raised pseudocapacitive capacitance and tensile strength. The solid polymer electrolyte was tuned to a gradient configuration, where it facilitated high ionic conductivity at the electrode-electrolyte interfaces and transitioned to a composition with high mechanical strength in the bulk for load support. The gradient design enabled the multilayer structural supercapacitors to reach state-of-the-art performance matching the level of monofunctional supercapacitors. In situ electrochemical-mechanical measurements established the device durability under mechanical loads. The structural supercapacitor was made into the hull of a model boat to demonstrate its multifunctionality.

This work studied a series of infrared detectors comprised of organic bulk heterojunctions to explain the origin of their broadband spectral response from the visible to the infrared spanning 1 to 8 μm and the transition from photonic to bolometric operation. Through comparisons of the detector current and the sub-bandgap density of states, the mid- and long-wave infrared response was attributed to charge trap-and-release processes that impact thermal charge generation and the activation energy of charge mobility. We further demonstrate how the sub-bandgap characteristics, mobility activation energy, and effective bandgap are key design parameters for controlling the device temperature coefficient of resistance, which reached up to -7%/K, better than other thin-film materials such as amorphous silicon and vanadium oxide.

Non-intrusive sensors that can be attached to marine species offer opportunities to study the impacts of environmental changes on their behaviors and well-being. This work presents a thin, flexible sensor tag to monitor the effects of dissolved oxygen and salinity on bivalve gape movement. The measurement range studied was 0.5-6 ppm for the dissolved oxygen sensor and 4-40 g kg -1 for the salinity sensor. The curvature strain sensor based on electrodeposited semiconducting fibers enabled measurements of an oyster's gape down to sub-mm displacement. The multiplexed sensors were fabricated by low-cost techniques, offering an economical and convenient platform for aquaculture studies.

The development of open-shell organic molecules that magnetically order at room temperature,which can be practically applied, remains a grand challenge in chemistry, physics, and materials science. Despite the exploration of vast chemical space, design paradigms for organic paramagnetic centers generally result in unpaired electron spins that are unstable or isotropic. Here, a high-spin conjugated polymer is demonstrated, which is composed of alternating cyclopentadithiophene and benzo[1,2-c;4,5-c']bis[1,2,5]thiadiazole heterocycles, in which macromolecular structure and topology coalesce to promote the spin center generation and intermolecular exchange coupling. Electron paramagnetic resonance (EPR) spectroscopy is consistent with spatially localized spins, while magnetic susceptibility measurements show clear anisotropic spin ordering and exchange interactions that persist at room temperature. The application of long-range π-correlations for spin center generation promotes remarkable stability. This work offers a fundamentally new approach to the implementation of this long-sought-after physical phenomenon within organic materials and the integration of manifold properties within emerging technologies., (© 2022 Wiley-VCH GmbH.)

Previous approaches to induce photomultiplication in organic diodes have increased the photosignal but lacked control over reducing background noise. This work presents a new interlayer design based on a heterojunction bilayer that concurrently enables photomultiplication and suppresses the dark current in organic shortwave infrared detectors to improve the overall detectivity. The heterojunction bilayer consists of a hole-transporting material copper thiocyanate and an electron-transporting material tin oxide, and this combination offers the ability to block charge injection in the dark. Under illumination, the bilayer promotes trap-assisted photomultiplication by lowering the tunneling barrier and amplifying the photocurrent through the injection of multiple carriers per absorbed photon. Upon incorporating the heterojunction interlayer in photodiodes and upconversion imagers, the devices achieve an external quantum efficiency up to 560% and a detectivity of 3.5 × 10 9 Jones. The upconversion efficiency of the imager doubles with a 1.7 fold improvement in contrast compared to the imager without the heterojunction interlayer. The new interlayer design is generalizable to work with different organic semiconductors, making it attractive and easy to integrate with emerging organic infrared systems.

Nitrate is an important marker of water quality that can be challenging to detect in seawater due to the presence of multiple chemical interferants and high background chloride. Here, we demonstrate a compact microfluidic device that incorporates electrochemical desalination to selectively remove the interfering chloride ions and improve the detection limit of the downstream potentiometric nitrate sensor. The microfluidic platform was fabricated by a low-cost cut-and-lamination approach, and the detection mechanism was based on potentiometric measurements at an Ag/AgCl electrode coated with a nitrate-selective membrane. The sensor system achieved a detection limit of 0.5 mM with a sensitivity of 11.3 mV/dec under continuous flow., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Compounds that exhibit spin-crossover (SCO) type behavior have been extensively investigated due to their ability to act as molecular switches. Depending on the coordinating ligand, in this case 1H -1,2,4-triazole, and the crystallite size of the SCO compound produced, the energy requirement for the spin state transition can vary. Here, SCO [Fe(Htrz) 2 (trz)](BF 4 )] nanoparticles were synthesized using modified reverse micelle methods. Reaction conditions and reagent ratios are strictly controlled to produce nanocubes of 40-50 nm in size. Decreases in energy requirements are seen in both thermal and magnetic transitions for the smaller sized crystallites, where, compared to bulk materials, a decrease of as much as 20 °C can be seen in low to high spin state transitions.

Synthetic aromatic polymers are ubiquitous and indispensable to modern life, industry, and the global economy. The direct functionalization of these materials remains a considerable challenge on account of their unreactive aromatic C-H bonds and robust physical properties. Here, we demonstrate that homogeneous gold catalysis offers a mild, chemoselective, and practical approach to functionalize high-volume commodity aromatic polymers. Utilizing a gold-catalyzed intermolecular hydroarylation between a methyl ester functionalized alkyne, methyl propiolate, and nucleophilic arenes within polystyrene (PS) results in direct functionalization of phenyl rings with 1,2-substituted methyl acrylate functional groups. The reactivity and functionalization depend on the steric and electronic environment of the catalyst, counterion pairing, and method of activation. The reactivity is broad in scope, enabling the functionalization of arenes within commercial polysulfone (PSU) and waste polyethylene terephthalate (PET). These reactions open new opportunities to chemically transform aromatic polymers and modify their physical properties., Competing Interests: The authors declare the following competing financial interest(s): E.R.K., S.B.H., and J.D.A. are inventors on a patent application filed by the University of Southern Mississippi for the reactions described in this Communication., (© 2021 The Authors. Published by American Chemical Society.)

Photodetection spanning the short-, mid-, and long-wave infrared (SWIR-LWIR) underpins modern science and technology. Devices using state-of-the-art narrow bandgap semiconductors require complex manufacturing, high costs, and cooling requirements that remain prohibitive for many applications. We report high-performance infrared photodetection from a donor-acceptor conjugated polymer with broadband SWIR-LWIR operation. Electronic correlations within the π-conjugated backbone promote a high-spin ground state, narrow bandgap, long-wavelength absorption, and intrinsic electrical conductivity. These previously unobserved attributes enabled the fabrication of a thin-film photoconductive detector from solution, which demonstrates specific detectivities greater than 2.10 × 10 9 Jones. These room temperature detectivities closely approach those of cooled epitaxial devices. This work provides a fundamentally new platform for broadly applicable, low-cost, ambient temperature infrared optoelectronics., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne-containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1-disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs., (© 2020 Wiley-VCH GmbH.)

Azo dyes are ubiquitous pollutants that contaminate water supplies and threaten human, biota, and ecosystem health. Their detection and discrimination are a considerable challenge owing to the numerous structural, chemical, and optical similarities between dyes, complexity of the wastewater in which they are found, and low environmental concentrations. Here, we demonstrate that the inner filter effect (IFE), in combination with conjugated polymer array-based sensing, offers a rapid approach for the quantitative profiling of these pollutants. The array was constructed using three anionic conjugated polyelectrolytes whose varying spectroscopic properties led to distinct IFE patterns in the presence of various dyes. These unique fluorescence response patterns were identified and processed using linear discriminant analysis (LDA), enabling the individual identification of 12 closely related azo dyes. To demonstrate the potential for utility in the environment, the array was used to differentiate between these dyes at nanomolar concentrations in water.

Sequence-controlled supramolecular polymers offer new design paradigms for generating stimuli-responsive macromolecules with enhanced functionalities. The dynamic character of supramolecular links present challenges to sequence definition in extended supramolecular macromolecules, and design principles remain nascent. Here, we demonstrate the first example of using stoichiometry-control to specify the monomer sequence in a linear supramolecular polymer by synthesizing both a homopolymer and an alternating copolymer from the same glycol-substituted cyanostar macrocycle and phenylene-linked diphosphate monomers. A 2:1 stoichiometry between macrocycle and diphosphate produces a supramolecular homopolymer of general formula ( A ) n comprised of repeating units of cyanostar-stabilized phosphate-phosphate dimers. Using a 1:1 stoichiometry, an alternating ( AB ) n structure is produced with half the phosphate dimers now stabilized by the additional counter cations that emerge hierarchically after forming the stronger cyanostar-stabilized phosphate dimers. These new polymer materials and binding motifs are sufficient to bear normal and shear stress to promote significant and tunable adhesive properties. The homopolymer ( A ) n , consisting of cyanostar-stabilized anti -electrostatic linkages, shows adhesion strength comparable to commercial superglue formulations based on polycyanoacrylate but is thermally reversible. Unexpectedly, and despite including traditional ionic linkages, the alternating copolymer ( AB ) n shows weaker adhesion strength more similar to commercial white glue based on poly(vinyl acetate). Thus, the adhesion properties can be tuned over a wide range by simply controlling the stoichiometric ratio of monomers. This study offers new insight into supramolecular polymers composed of custom-designed anion and receptor monomers and demonstrates the utility of emerging functional materials based on anion-anion linkages.

This report demonstrates high-performance infrared phototransistors that use a broad-band absorbing organic bulk heterojunction (BHJ) layer responsive from the visible to the shortwave infrared, from 500 to 1400 nm. The device structure is based on a bilayer transistor channel that decouples charge photogeneration and transport, enabling independent optimization of each process. The organic BHJ layer is improved by incorporating camphor, a highly polarizable additive that increases carrier lifetime. An indium zinc oxide transport layer with high electron mobility is employed for rapid charge transport. As a result, the phototransistors achieve a dynamic range of 127 dB and reach a specific detectivity of 5 × 10 12 Jones under a low power illumination of 20 nW/cm 2 , outperforming commercial germanium photodiodes in the spectral range below 1300 nm. The photodetector metrics are measured with respect to the applied voltage, incident light power, and temporal bandwidth, demonstrating operation at a video-frame rate of 50 Hz. In particular, the frequency and light dependence of the phototransistor characteristics are analyzed to understand the change in photoconductive gain under different working conditions.

Natural and anthropogenic activities result in the production of polycyclic aromatic hydrocarbons (PAHs), persistent pollutants that negatively impact the environment and human health. Rapid and reliable methods for the detection and discrimination of these compounds remains a technological challenge owing to their relatively featureless properties, structural similarities, and existence as complex mixtures. Here, we demonstrate that the inner filter effect (IFE), in combination with conjugated polymer (CP) array-based sensing, offers a straightforward approach for the quantitative and qualitative profiling of PAHs. The sensor array was constructed from six fluorescent fluorene-based copolymers, which incorporate side chains with peripheral 2-phenylbenzimidazole substituents that provide spectral overlap with PAHs and give rise to a pronounced IFE. Subtle structural differences in copolymer structure result in distinct spectral signatures, which provide a unique "chemical fingerprint" for each PAH. The discriminatory power of the array was evaluated using linear discriminant analysis (LDA) and principal component analysis (PCA) in order to discriminate between 16 PAH compounds identified as priority pollutants by the US Environmental Protection Agency (EPA). This array is the first multivariate system reliant on the modulation of the spectral signatures of CPs through the IFE for the detection and discrimination of closely related polynuclear aromatic species., (This journal is © The Royal Society of Chemistry 2019.)

Supramolecular polymers have enabled far-reaching fundamental science and the development of diverse macromolecular technologies owing to the reversible and noncovalent chemical connectivities that define their properties. Despite the unabated development of these materials using highly tailorable recognition elements, anion-based polymers remain rare as a result of the weak interactions they mediate. Here, we use design rules inspired by cation-driven polymers to demonstrate a new noncovalent link based on receptor-stabilized anion-anion interactions that enables the efficient linear polymerization of simple difunctional phosphonates. The linear main chain connectivity and molecular topology were confirmed by single crystal X-ray diffraction, which demonstrates the rare 2:2 stoichiometry between the anionic phosphonate end groups and a pair of π-stacked cyanostar macrocycles. The stability of these links enables rapid polymerization of difunctional phosphonates employing different aliphatic linkers (C 6 H 12 , C 8 H 16 , C 10 H 20 , C 12 H 24 ). Diphosphonates with greater chain flexibility (C 12 H 24 ) enable greater polymerization with an average degree of polymerization of nine emerging at 10 mM. Viscosity measurements show a transition from oligomers to polymers at the critical polymerization concentration of 5 mM. In a rare correlation, NMR spectroscopy shows a coincident molecular signature of the polymerization at 5 mM. These polymers are highly concentration dependent, reversibly polymerize with acid and base, and respond to competitive anions. They display the design simplicity of metallo-supramolecular polymers with transfer of the strong 2:2 recognition chemistry to macromolecules. The simplicity and understanding of this new class of supramolecular polymer is anticipated to open opportunities in tailoring anion-based functional materials.

Infrared photodetectors are essential to many applications, including surveillance, communications, process monitoring, and biological imaging. The short-wave infrared (SWIR) spectral region (λ = 1-3 μm) is particularly powerful for health monitoring and medical diagnostics because biological tissues show low absorbance and minimal SWIR autofluorescence, enabling greater penetration depth and improved resolution in comparison with visible light. However, current SWIR photodetection technologies are largely based on epitaxially grown inorganic semiconductors, which are costly, require complex processing, and impose cooling requirements incompatible with wearable electronics. Solution-processable semiconductors are being developed for infrared detectors to enable low-cost direct deposition and facilitate monolithic integration and resolution not achievable using current technologies. In particular, organic semiconductors offer numerous advantages, including large-area and conformal coverage, temperature insensitivity, and biocompatibility, for enabling ubiquitous SWIR optoelectronics. This Account introduces recent efforts to advance the spectral response of organic photodetectors into the SWIR. High-performance visible to near-infrared (NIR) organic photodetectors have been demonstrated by leveraging the wealth of knowledge from organic solar cell research in the past decade. On the other hand, organic semiconductors that absorb in the SWIR are just emerging, and only a few organic materials have been reported that exhibit photocurrent past 1 μm. In this Account, we survey novel SWIR molecules and polymers and discuss the main bottlenecks associated with charge recombination and trapping, which are more challenging to address in narrow-band-gap photodetectors in comparison with devices operating in the visible to NIR. As we call attention to discrepancies in the literature regarding performance metrics, we share our perspective on potential pitfalls that may lead to overestimated values, with particular attention to the detectivity (signal-to-noise ratio) and temporal characteristics, in order to ensure a fair comparison of device performance. As progress is made toward overcoming challenges associated with losses due to recombination and increasing noise at progressively narrower band gaps, the performance of organic SWIR photodetectors is steadily rising, with detectivity exceeding 10 11 Jones, comparable to that of commercial germanium photodiodes. Organic SWIR photodetectors can be incorporated into wearable physiological monitors and SWIR spectroscopic imagers that enable compositional analysis. A wide range of potential applications include food and water quality monitoring, medical and biological studies, industrial process inspection, and environmental surveillance. There are exciting opportunities for low-cost organic SWIR technologies to be as widely deployable and affordable as today's ubiquitous cell phone cameras operating in the visible, which will serve as an empowering tool for users to discover information in the SWIR and inspire new use cases and applications.

The chemical doping reaction of P3HT with F 4 -TCNQ was studied by optical absorption spectroscopy, atomic force microscopy, and Kelvin probe force microscopy. We demonstrate that P3HT aggregation preferentially occurs before the actual charge transfer step takes place, emphasizing the impact of morphology on the chemical doping reaction of conjugated polymers at the molecular level.

Four organic sensitizers incorporating a cross-conjugated cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) π-bridge have been synthesized. As a result of molecular engineering, broad high energy bands and red shifted absorption maxima and onset is observed relative to a benchmark analogue (C218) using a non-cross-conjugated CPDT π-bridge. The use of a cross-conjugated bridge allows a new strategy for tuning dye energetics and introduction of increased absorption uniformity by adding additional high-energy absorption bands. These dyes show solar-to-electric conversion up to 800 nm with one derivative exceeding the performance of C218 under identical conditions.

Bulk heterojunction photodiodes are fabricated using a new donor-acceptor polymer with a near-infrared absorption edge at 1.2 μm, achieving a detectivity up to 10 12 Jones at a wavelength of 1 μm and an excellent linear dynamic range of 86 dB. The photodiode detectivity is maximized by operating at zero bias to suppress dark current, while a thin 175 nm active layer is used to facilitate charge collection without reverse bias. Analysis of the temperature dependence of the dark current and spectral response demonstrates a 2.8-fold increase in detectivity as the temperature was lowered from 44 to -12 °C, a relatively small change when compared to that of inorganic-based devices. The near-infrared photodiode shows a switching speed reaching up to 120 μs without an external bias. An application using our NIR photodiode to detect arterial pulses of a fingertip is demonstrated.

Bridgehead imine-substituted cyclopentadithiophene structural units, in combination with highly electronegative acceptors that exhibit progressively delocalized π-systems, afford donor-acceptor (DA) conjugated polymers with broad absorption profiles that span technologically relevant wavelength (λ) ranges from 0.7 < λ < 3.2 μm. A joint theoretical and experimental study demonstrates that the presence of the cross-conjugated substituent at the donor bridgehead position results in the capability to fine-tune structural and electronic properties so as to achieve very narrow optical bandgaps (Eg (opt) < 0.5 eV). This strategy affords modular DA copolymers with broad- and long-wavelength light absorption in the infrared and materials with some of the narrowest bandgaps reported to date., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A nickel alpha-keto-beta-diimine initiator can be activated using treated methylaluminoxane (MAO) to generate active sites capable of the polymerization of ethylene, propene and 1-hexene under living conditions.

A semicrystalline polyethylene (PE) macroinitiator was prepared by copolymerizing ethylene and an inititating monomer (5-norbornen-2-yl-2'-bromo-2'-methyl propanoate) (3) using [N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)isobutanamidato]-Ni(eta1-CH2Ph)(PMe3) (1) and Ni(COD)2 (bis(1,5-cyclooctadiene)-nickel) (2). Although 3 decomposes Ni(COD)2, if the initiating species (1/2) are exposed to ethylene for a period of time, t1, and then 3 is introduced for another period of time, t2, the polymerization takes place in a controlled manner. Variations in temperature, pressure, and [3] afford a great deal of control over the composition and architecture of the PE macroinitiator. Subsequent grafting with methyl methacrylate (MMA) yields PE-graft-PMMA with narrow polydispersities and increasing PMMA content at longer reaction times. Because the products are semicrystalline materials with high melting points, they are anticipated to function as blend compatibilizers for linear polyethylene.