Triplet-pair spin signatures from macroscopically aligned heteroacenes in an oriented single crystal.

The photo-driven process of singlet fission generates coupled triplet pairs (TT) with fundamentally intriguing and potentially useful properties. The quintet 5TT0 sublevel is particularly interesting for quantum information because it is highly entangled, is addressable with microwave pulses, and could be detected using optical techniques. Previous theoretical work on a model Hamiltonian and nonadiabatic transition theory, called the JDE model, has determined that this sublevel can be selectively populated if certain conditions are met. Among the most challenging, the molecules within the dimer undergoing singlet fission must have their principal magnetic axes parallel to one another and to an applied Zeeman field. Here, we present time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy of a single crystal sample of a tetracenethiophene compound featuring arrays of dimers aligned in this manner, which were mounted so that the orientation of the field relative to the molecular axes could be controlled. The observed spin sublevel populations in the paired TT and unpaired (T+T) triplets are consistent with predictions from the JDE model, including preferential 5TT0 formation at z ‖ B0, with one caveat-two 5TT spin sublevels have little to no population. This may be due to crossings between the 5TT and 3TT manifolds in the field range investigated by TR-EPR, consistent with the intertriplet exchange energy determined by monitoring photoluminescence at varying magnetic fields.

Investigating the Mechanism of Aluminum Fluoride Chelation.

Aluminum fluoride (AlF) complexes have been used over the past decade to incorporate [18F]fluoride into large biomolecules in a highly selective fashion by using relatively facile conditions. However, despite their widespread usage, there are a large number of variations in the reaction conditions, without a definitive discussion provided on the mechanism to understand how these changes would alter the end result. Herein, we report a detailed mechanistic investigation of the reaction, using a mixture of theoretical studies, fluorine-19 and fluorine-18 chemistry, and the consequences it has on the efficient clinical translation of AlF-containing imaging agents.

Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer.

Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

The Influence of Regiochemistry on the Performance of Organic Mixed Ionic and Electronic Conductors.

Thiophenes functionalised in the 3-position are ubiquitous building blocks for the design and synthesis of organic semiconductors. Their non-centrosymmetric nature has long been used as a powerful synthetic design tool exemplified by the vastly different properties of regiorandom and regioregular poly(3-hexylthiophene) owing to the repulsive head-to-head interactions between neighbouring side chains in the regiorandom polymer. The renewed interest in highly electron-rich 3-alkoxythiophene based polymers for bioelectronic applications opens up new considerations around the regiochemistry of these systems as both the head-to-tail and head-to-head couplings adopt near-planar conformations due to attractive intramolecular S-O interactions. To understand how this increased flexibility in the molecular design can be used advantageously, we explore in detail the geometrical and electronic effects that influence the optical, electrochemical, structural, and electrical properties of a series of six polythiophene derivatives with varying regiochemistry and comonomer composition. We show how the interplay between conformational disorder, backbone coplanarity and polaron distribution affects the mixed ionic-electronic conduction. Ultimately, we use these findings to identify a new conformationally restricted polythiophene derivative for p-type accumulation-mode organic electrochemical transistor applications with performance on par with state-of-the-art mixed conductors evidenced by a µC* product of 267 F V-1 cm-1 s-1 .

Optical readout of singlet fission biexcitons in a heteroacene with photoluminescence detected magnetic resonance.

Molecular spin systems based on photoexcited triplet pairs formed via singlet fission (SF) are attractive as carriers of quantum information because of their potentially pure and controllable spin polarization, but developing systems that offer optical routes to readout as well as initialization is challenging. Herein, we characterize the electron spin magnetic resonance change in the photoluminescence intensity for a tailored organic molecular crystal while sweeping a microwave drive up to 10 GHz in a broadband loop structure. We observe resonant transitions for both triplet and quintet spin sublevel populations showing their optical sensitivity and revealing the zero-field parameters for each. We map the evolution of these spectra in both microwave frequency and magnetic field, producing a pattern of optically detected magnetic resonance (ODMR) peaks. Fits to these data using a suitable model suggest significant spin polarization in this system with orientation selectivity. Unusual excitation intensity dependence is also observed, which inverts the sign of the ODMR signal for the triplet features, but not for the quintet. These observations demonstrate optical detection of the spin sublevel population dictated by SF and intermolecular geometry, and highlight anisotropic and multi-scale dynamics of triplet pairs.

Regiochemistry-Driven Organic Electrochemical Transistor Performance Enhancement in Ethylene Glycol-Functionalized Polythiophenes.

Novel p-type semiconducting polymers that can facilitate ion penetration, and operate in accumulation mode are much desired in bioelectronics. Glycol side chains have proven to be an efficient method to increase bulk electrochemical doping and optimize aqueous swelling. One early polymer which exemplifies these design approaches was p(g2T-TT), employing a bithiophene-co-thienothiophene backbone with glycol side chains in the 3,3' positions of the bithiophene repeat unit. In this paper, the analogous regioisomeric polymer, namely pgBTTT, was synthesized by relocating the glycol side chains position on the bithiophene unit of p(g2T-TT) from the 3,3' to the 4,4' positions and compared with the original p(g2T-TT). By changing the regio-positioning of the side chains, the planarizing effects of the S-O interactions were redistributed along the backbone, and the influence on the polymer's microstructure organization was investigated using grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The newly designed pgBTTT exhibited lower backbone disorder, closer π-stacking, and higher scattering intensity in both the in-plane and out-of-plane GIWAXS measurements. The effect of the improved planarity of pgBTTT manifested as higher hole mobility (µ) of 3.44 ± 0.13 cm2 V-1 s-1. Scanning tunneling microscopy (STM) was in agreement with the GIWAXS measurements and demonstrated, for the first time, that glycol side chains can also facilitate intermolecular interdigitation analogous to that of pBTTT. Electrochemical quartz crystal microbalance with dissipation of energy (eQCM-D) measurements revealed that pgBTTT maintains a more rigid structure than p(g2T-TT) during doping, minimizing molecular packing disruption and maintaining higher hole mobility in operation mode.

Modification of Indacenodithiophene-Based Polymers and Its Impact on Charge Carrier Mobility in Organic Thin-Film Transistors.

The polymer indacenodithiophene-co-benzothiadiazole (IDT-BT) has been thoroughly studied for its use in p-type organic thin-film transistors over the course of the past decade. While a variety of modifications have been made to its structure, few analogues have been able to match or surpass the hole mobility that can be obtained by IDT-BT. Here, we discuss the rationale behind the chemical modifications that have been utilized and suggest design principles toward high-mobility indacenodithiophene-based polymers. It is clear that planarizing intramolecular interactions, which exist between the peripheral thiophene of the IDT unit and the benzothiadiazole, are imperative for achieving high hole mobilities in this relatively amorphous polymer. Moreover, despite the less ordered backbones of the extended fused-ring cores that have recently been utilized (TIF-BT and TBIDT-BT), high mobilities were still attained in these polymers owing to additional interchain charge transfer. Thus, maintaining the beneficial thiophene-benzothiadiazole intramolecular interactions, while further extending the IDT core to promote interchain charge transfer, is a logical strategy toward high-mobility p-type polymers.

The Effect of Ring Expansion in Thienobenzo[b]indacenodithiophene Polymers for Organic Field-Effect Transistors.

A fused donor, thienobenzo[b]indacenodithiophene (TBIDT), was designed and synthesized using a novel acid-promoted cascade ring closure strategy, and then copolymerized with a benzothiadiazole (BT) monomer. The backbone of TBIDT is an expansion of the well-known indacenodithiophene (IDT) unit and was expected to enhance the charge carrier mobility by improving backbone planarity and facilitating short contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.9 cm2 V-1 s-1, lower than the performance of IDT-BT (∼1.5 cm2 V-1 s-1). Mobilities extracted from time-resolved microwave conductivity measurements were consistent with the trend in hole mobilities in organic field-effect transistor devices. Scanning tunneling microscopy measurements and computational modeling illustrated that TBIDT-BT exhibits a less ordered microstructure in comparison to IDT-BT. This reveals that a regular side-chain packing density, independent of conformational isomers, is critical to avoid local free volume due to irregular packing, which can host trapping impurities. DFT calculations indicated that TBIDT-BT, despite containing a larger, planar unit, showed less stabilization of planar backbone geometries in comparison to IDT-BT. This is due to the reduced electrostatic stabilizing interactions between the peripheral thiophene of the fused core and the BT unit, resulting in a reduction of the barrier to rotation around the single bond. These insights provide a greater understanding of the general structure-property relationships required for semiconducting polymer repeat units to ensure optimal backbone planarization, as illustrated with IDT-type units, guiding the design of novel semiconducting polymers with extended fused backbones for high-performance field-effect transistors.

Conformational Analysis of Conjugated Organic Materials: What Are My Heteroatoms Really Doing?

Organic semiconductor small molecules and polymers often incorporate heteroatoms into their chemical structures to affect the electronic properties of the material. A particular design philosophy has been to use these heteroatoms to influence torsional potentials, since the overlap of adjacent π-orbitals is most efficient in planar systems and is critical for charge delocalization in these systems. Since these design rules became popular, the messages from the earlier works have become lost in a sea of reports of "conformational locks", where the non-covalent interactions have relatively small contributions to planarizing torsional potentials. Greater influences can be found in the stabilization by extended conjugation, consideration of steric repulsion, and the interactions involving solubilizing chains and neighboring molecules or polymer chains in condensed phases.

Understanding radiation-generated electronic traps in radiation dosimeters based on organic field-effect transistors.

Organic dosimeters offer unique advantages over traditional technologies, and they can be used to expand the capabilities of current radiation detection systems. In-depth knowledge of the mechanisms underlying the interaction between radiation and organic materials is essential for their widespread adoption. Here, we identified and quantitatively characterized the electronic traps generated during the operation of radiation dosimeters based on organic field-effect transistors. Spectral analysis of the trap density of states, along with optical and structural studies, revealed the origin of trap states as local structural disorder within the crystalline films. Our results provide new insights into the radiation-induced defects in organic dosimeters, and pave the way for the development of more efficient and reliable radiation detection devices.

Cyanine-like dyes with large bond-length alternation.

Herein, the synthesis and properties of alkyne-bridged carbocations, which are analogous in structure to cyanine dyes, are reported. An alkene-bridged dye, linked at the third position of the indole, was also synthesized as a reference compound. These new carbocations are stable under ambient conditions, allowing characterization by UV/Vis and NMR ((1)H and (13)C) spectroscopies. These techniques revealed a large degree of delocalization of the positive charge, similar to a previously reported porphyrin carbocation. The linear and nonlinear optical properties are compared with cyanine dyes and triarylmethyl cations, to investigate the effects of the bond-length alternation and the overall molecular geometry. The value of Re(γ), the real part of the third-order microscopic polarizability, of -1.3×10(-33)  esu for the alkyne-linked cation is comparable to that of a cyanine dye of similar length. Nondegenerate two-photon absorption spectra showed that the alkene-bridged dye exhibited characteristics of cyanines, whereas the alkyne-bridged dye is reminiscent of octupolar chromophores, such as the triarylmethyl carbocation brilliant green. Such attributes were confirmed and rationalized by quantum chemical calculations.

Estimation of Polaron Delocalization Lengths in Conjugated Organic Polymers.

Organic conjugated polymers have been pivotal in the development of organic electronics in applications such as in organic field effect transistors and photovoltaics. In these applications, the electronic structures of the polymers change by the gain or loss of charge. In this work, the visualization of charge delocalization in oligomeric and polymeric systems by range-separated density functional theory calculations reveals an efficient method of determining the polymer limit and polaron delocalization lengths of conjugated systems. Methods of displaying these data and the important computational details of the calculations are explored. These calculations provide researchers information about intrachain charge transport, donor-acceptor characteristics, and a method of validating that the computational model structures are indeed representative of the polymer and not just small molecules. Contributions from differing co-monomers to the polymer properties can be assessed through plotting the charge distributions along the polymer backbone. Visualization of polaron (de)localization can guide future polymer design, e.g., by placement of solubilizing chains to aid interchain interactions at polymer sections bearing greater polaron localization, or by minimizing charge accumulation at potentially reactive monomer units.

Near-Infrared Absorption Features of Triplet-Pair States Assigned by Photoinduced-Absorption-Detected Magnetic Resonance.

Singlet fission proceeds through a manifold of triplet-pair states that are exceedingly difficult to distinguish spectroscopically. Here, we introduce a new implementation of photoinduced-absorption-detected magnetic resonance (PADMR) and use it to understand the excited-state absorption spectrum of a tri-2-pentylsilylethynyl pentadithiophene (TSPS-PDT) film. These experiments allow us to directly correlate magnetic transitions driven by RF with electronic transitions in the visible and near-infrared spectrum with high sensitivity. We find that the new near-infrared excited-state transitions that arise in thin films of TSPS-PDT are correlated with the magnetic transitions of T1, not 5TT. Thus, we assign these features to the excited-state absorption of 1TT, which is depleted when T1 states are driven to a spin configuration that forbids subsequent fusion. These results clarify the disputed origin of triplet-associated near-infrared absorption features in singlet-fission materials and demonstrate an incisive general purpose tool for studying the evolution of high-spin excited states.

The Influence of Regiochemistry on the Performance of Organic Mixed Ionic and Electronic Conductors.

Thiophenes functionalised in the 3-position are ubiquitous building blocks for the design and synthesis of organic semiconductors. Their non-centrosymmetric nature has long been used as a powerful synthetic design tool exemplified by the vastly different properties of regiorandom and regioregular poly(3-hexylthiophene) owing to the repulsive head-to-head interactions between neighbouring side chains in the regiorandom polymer. The renewed interest in highly electron-rich 3-alkoxythiophene based polymers for bioelectronic applications opens up new considerations around the regiochemistry of these systems as both the head-to-tail and head-to-head couplings adopt near-planar conformations due to attractive intramolecular S-O interactions. To understand how this increased flexibility in the molecular design can be used advantageously, we explore in detail the geometrical and electronic effects that influence the optical, electrochemical, structural, and electrical properties of a series of six polythiophene derivatives with varying regiochemistry and comonomer composition. We show how the interplay between conformational disorder, backbone coplanarity and polaron distribution affects the mixed ionic-electronic conduction. Ultimately, we use these findings to identify a new conformationally restricted polythiophene derivative for p-type accumulation-mode organic electrochemical transistor applications with performance on par with state-of-the-art mixed conductors evidenced by a µC* product of 267 F V-1 cm-1 s-1.

Elucidating Design Rules toward Enhanced Solid-State Charge Transport in Oligoether-Functionalized Dioxythiophene-Based Alternating Copolymers.

This study investigates the solid-state charge transport properties of the oxidized forms of dioxythiophene-based alternating copolymers consisting of an oligoether-functionalized 3,4-propylenedioxythiophene (ProDOT) copolymerized with different aryl groups, dimethyl ProDOT (DMP), 3,4-ethylenedioxythiophene (EDOT), and 3,4-phenylenedioxythiophene (PheDOT), respectively, to yield copolymers P(OE3)-D, P(OE3)-E, and P(OE3)-Ph. At a dopant concentration of 5 mM FeTos3, the electrical conductivities of these copolymers vary significantly (ranging between 9 and 195 S cm-1) with the EDOT copolymer, P(OE3)-E, achieving the highest electrical conductivity. UV-vis-NIR and X-ray spectroscopies show differences in both susceptibility to oxidative doping and extent of oxidation for the P(OE3) series, with P(OE3)-E being the most doped. Wide-angle X-ray scattering measurements indicate that P(OE3)-E generally demonstrates the lowest paracrystallinity values in the series, as well as relatively small π-π stacking distances. The significant (i.e., order of magnitude) increase in electrical conductivity of doped P(OE3)-E films versus doped P(OE3)-D or P(OE3)-Ph films can therefore be attributed to P(OE3)-E exhibiting both the highest carrier ratios in the P(OE3) series, along with good π-π overlap and local ordering (low paracrystallinity values). Furthermore, these trends in the extent of doping and paracrystallinity are consistent with the reduced Fermi energy level and transport function prefactor parameters calculated using the semilocalized transport (SLoT) model. Observed differences in carrier ratios at the transport edge (ct) and reduced Fermi energies [η(c)] suggest a broader electronic band (better overlap and more delocalization) for the EDOT-incorporating P(OE3)-E polymer relative to P(OE3)-D and P(OE3)-Ph. Ultimately, we rationalize improvements in electrical conductivity due to microstructural and doping enhancements caused by EDOT incorporation, a structure-property relationship worth considering in the future design of highly electrically conductive systems.

From p- to n-Type Mixed Conduction in Isoindigo-Based Polymers through Molecular Design.

Organic mixed ionic and electronic conductors are of significant interest for bioelectronic applications. Here, three different isoindigoid building blocks are used to obtain polymeric mixed conductors with vastly different structural and electronic properties which can be further fine-tuned through the choice of comonomer unit. This work shows how careful design of the isoindigoid scaffold can afford highly planar polymer structures with high degrees of electronic delocalization, while subtle structural modifications can control the dominant charge carrier (hole or electron) when probed in organic electrochemical transistors. A combination of experimental and computational techniques is employed to probe electrochemical, structural, and mixed ionic and electronic properties of the polymer series which in turn allows the derivation of important structure-property relations for this promising class of materials in the context of organic bioelectronics. Ultimately, these findings are used to outline robust molecular-design strategies for isoindigo-based mixed conductors that can support efficient p-type, n-type, and ambipolar transistor operation in an aqueous environment.

Suppressing bias stress degradation in high performance solution processed organic transistors operating in air.

Solution processed organic field effect transistors can become ubiquitous in flexible optoelectronics. While progress in material and device design has been astonishing, low environmental and operational stabilities remain longstanding problems obstructing their immediate deployment in real world applications. Here, we introduce a strategy to identify the most probable and severe degradation pathways in organic transistors and then implement a method to eliminate the main sources of instabilities. Real time monitoring of the energetic distribution and transformation of electronic trap states during device operation, in conjunction with simulations, revealed the nature of traps responsible for performance degradation. With this information, we designed the most efficient encapsulation strategy for each device type, which resulted in fabrication of high performance, environmentally and operationally stable small molecule and polymeric transistors with consistent mobility and unparalleled threshold voltage shifts as low as 0.1 V under the application of high bias stress in air.

Resolving electron injection from singlet fission-borne triplets into mesoporous transparent conducting oxides.

Photoinduced electron transfer into mesoporous oxide substrates is well-known to occur efficiently for both singlet and triplet excited states in conventional metal-to-ligand charge transfer (MLCT) dyes. However, in all-organic dyes that have the potential for producing two triplet states from one absorbed photon, called singlet fission dyes, the dynamics of electron injection from singlet vs. triplet excited states has not been elucidated. Using applied bias transient absorption spectroscopy with an anthradithiophene-based chromophore (ADT-COOH) adsorbed to mesoporous indium tin oxide (nanoITO), we modulate the driving force and observe changes in electron injection dynamics. ADT-COOH is known to undergo fast triplet pair formation in solid-state films. We find that the electronic coupling at the interface is roughly one order of magnitude weaker for triplet vs. singlet electron injection, which is potentially related to the highly localized nature of triplets without significant charge-transfer character. Through the use of applied bias on nanoITO:ADT-COOH films, we map the electron injection rate constant dependence on driving force, finding negligible injection from triplets at zero bias due to competing recombination channels. However, at driving forces greater than -0.6 eV, electron injection from the triplet accelerates and clearly produces a trend with increased applied bias that matches predictions from Marcus theory with a metallic acceptor.

Extending conjugation in porphyrin dimer carbocations.

The addition of alkynyl porphyrins to carbonyl compounds was used to prepare a series of porphyrin dimer tertiary alcohols. Treatment of these alcohols with acid gave conjugated carbocations with three to nine carbon atoms bridging between the porphyrins. All these carbocations show strong absorption in the near-IR region between 1000-1800 nm. The absorption spectra exhibit a length-dependence similar to that of polymethine cyanines, with a bathochromic shift of approximately 200 nm (900 cm(-1)) per alkyne. The longest of these chromophores has an absorption maximum at 1623 nm (in CHCl(3) with 2% trifluoroacetic acid). The symmetry of the pi-system has a strong effect on the position, intensity and width of the absorption bands. The stability of the cations in solution decreases with increasing bridge length.

In Situ Reduction and Functionalization of Polycyclic Quinones.

Attempts to functionalize polycyclic quinones using lithium diisopropylamide as a base led to the unexpected formation of acenes. This reaction proceeds by electron transfer from the base to the electron deficient quinone, whose radical anion can react with a variety of electrophiles. Siloxy derivatives synthesized by this method could be easily isolated but showed poor photostability. In situ reduced intermediate generation is a convenient approach to functionalization of oxidatively unstable hydroquinones.