Near-infrared luminescent open-shell π-conjugated systems with a bright lowest-energy zwitterionic singlet excited state.

Open-shell systems with extensive π-conjugation have fascinating properties due to their narrow bandgaps and spin interactions. In this work, we report neutral open-shell di- and polyradical conjugated materials exhibiting intriguing optical and magnetic properties. Our key design advance is the planarized geometry allowing for greater interaction between adjacent spins. This results in absorption and emission in the near infrared at 803 and 1050 nanometers, respectively, and we demonstrate a unique electronic structure where a bright zwitterionic excited state is the lowest-accessible electronic transition. Electron paramagnetic resonance spectroscopy and superconducting quantum interference device measurements reveal that our materials are open-shell singlets with different degrees of spin interactions, dynamics, and antiferromagnetic properties, which likely contributed to the formation of their emissive zwitterionic singlet excited state and near-infrared emission. In addition, our materials show reversible and stable electrochromic switching with more than 500 cycles, indicating their potential for optoelectronic and electrochemical energy storage applications.

Classification and quantitative characterisation of the excited states of π-conjugated diradicals.

Diradicals are of high current interest as emerging materials for next generation optoelectronic applications. To tune their excited-state properties it would be greatly beneficial to have a detailed understanding of the wave functions of the different states involved but this endeavour is hampered by formal and practical barriers. To tackle these challenges, we present a formal analysis as well as concrete results on diradical excited states. We start with a detailed investigation of the available states of a two-orbital two-electron model viewed from both the valence-bond and molecular orbital perspectives. We highlight the presence of diradical and zwitterionic states and illustrate their connections to the states found in closed-shell molecules. Subsequently, we introduce practical protocols for analysing states from realistic multireference computations applying these to the para-quinodimethane (pQDM) molecule. The analysis reveals four different categories of states - diradical, zwitterionic, HOMO-SOMO as well as biexciton - while also providing insight into their energetics and optical properties. Twisting the CH2 groups allows us to interconvert between the closed- and open-shell forms of pQDM illustrating the connection between the states in both forms. More generally, we hope that this work will lay the foundations for a more powerful rational design approach to diradicals for photophysical applications.

Singlet Fission in Pechmann Dyes: Planar Chromophore Design and Understanding.

Singlet fission in organic chromophores holds the potential for enhancing photovoltaic efficiencies beyond the single-junction limit. The most basic requirement of a singlet fission material is that it has a large energy gap between its first singlet and triplet excited states. Identifying such compounds is not simple and has been accomplished either through computational screening or by subtle modifications of previously known fission materials. Here, we propose an approach that leverages ground and excited-state aromaticity combined with double-bond conformation to establish simple qualitative design rules for predicting fundamental optical properties without the need for computational modeling. By investigating two Pechmann dye isomers, we demonstrate that although their planarity and degree of charge transfer are similar, singlet fission is active in the isomer with a trans-conformation, while the cis-isomer exhibits greater favorability for polaronic processes, experimentally validated using ultrafast and electron spin resonance spectroscopy. Our results offer a new design perspective that provides a rational framework for tailoring optoelectronic systems to specific applications such as singlet fission or triplet-triplet annihilation.

Decoupling excitons from high-frequency vibrations in organic molecules.

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon-carbon stretch modes (1,000-1,600 cm-1) has been thought to be unavoidable1,2. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton-vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680-800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm-1, frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

Steric Control of Luminescence in Phenyl-Substituted Trityl Radicals.

Triphenylmethyl (trityl) radicals have shown potential for use in organic optoelectronic applications, but the design of practical trityl structures has been limited to donor/radical charge-transfer systems due to the poor luminescence of alternant symmetry hydrocarbons. Here, we circumvent the symmetry-forbidden transition of alternant hydrocarbons via excited-state symmetry breaking in a series of phenyl-substituted tris(2,4,6-trichlorophenyl)methyl (TTM) radicals. We show that 3-fold phenyl substitution enhances the emission of the TTM radical and that steric control modulates the optical properties in these systems. Simple ortho-methylphenyl substitution boosts the photoluminescence quantum efficiency from 1% (for TTM) to 65% at a peak wavelength of 612 nm (for 2-T3TTM) in solution. In the crystalline solid state, the neat 2-T3TTM radical shows a remarkably high photoluminescence quantum efficiency of 25% for emission peaking at 706 nm. This has implications in the design of aryl-substituted radical structures where the electronic coupling of the substituents influences variables such as emission, charge transfer, and spin interaction.

Inverted device architecture for high efficiency single-layer organic light-emitting diodes with imbalanced charge transport.

Many wide-gap organic semiconductors exhibit imbalanced electron and hole transport, therefore efficient organic light-emitting diodes require a multilayer architecture of electron- and hole-transport materials to confine charge recombination to the emissive layer. Here, we show that even for emitters with imbalanced charge transport, it is possible to obtain highly efficient single-layer organic light emitting diodes (OLEDs), without the need for additional charge-transport and blocking layers. For hole-dominated emitters, an inverted single-layer device architecture with ohmic bottom-electron and top-hole contacts moves the emission zone away from the metal top electrode, thereby more than doubling the optical outcoupling efficiency. Finally, a blue-emitting inverted single-layer OLED based on thermally activated delayed fluorescence is achieved, exhibiting a high external quantum efficiency of 19% with little roll-off at high brightness, demonstrating that balanced charge transport is not a prerequisite for highly efficient single-layer OLEDs.

Ligand-Directed Self-Assembly of Organic-Semiconductor/Quantum-Dot Blend Films Enables Efficient Triplet Exciton-Photon Conversion.

Blends comprising organic semiconductors and inorganic quantum dots (QDs) are relevant for many optoelectronic applications and devices. However, the individual components in organic-QD blends have a strong tendency to aggregate and phase-separate during film processing, compromising both their structural and electronic properties. Here, we demonstrate a QD surface engineering approach using electronically active, highly soluble semiconductor ligands that are matched to the organic semiconductor host material to achieve well-dispersed inorganic-organic blend films, as characterized by X-ray and neutron scattering, and electron microscopies. This approach preserves the electronic properties of the organic and QD phases and also creates an optimized interface between them. We exemplify this in two emerging applications, singlet-fission-based photon multiplication (SF-PM) and triplet-triplet annihilation-based photon upconversion (TTA-UC). Steady-state and time-resolved optical spectroscopy shows that triplet excitons can be transferred with near unity efficiently across the organic-inorganic interface, while the organic films maintain efficient SF (190% yield) in the organic phase. By changing the relative energy between organic and inorganic components, yellow upconverted emission is observed upon 790 nm NIR excitation. Overall, we provide a highly versatile approach to overcome longstanding challenges in the blending of organic semiconductors with QDs that have relevance for many optical and optoelectronic applications.

Suppression of Dexter transfer by covalent encapsulation for efficient matrix-free narrowband deep blue hyperfluorescent OLEDs.

Hyperfluorescence shows great promise for the next generation of commercially feasible blue organic light-emitting diodes, for which eliminating the Dexter transfer to terminal emitter triplet states is key to efficiency and stability. Current devices rely on high-gap matrices to prevent Dexter transfer, which unfortunately leads to overly complex devices from a fabrication standpoint. Here we introduce a molecular design where ultranarrowband blue emitters are covalently encapsulated by insulating alkylene straps. Organic light-emitting diodes with simple emissive layers consisting of pristine thermally activated delayed fluorescence hosts doped with encapsulated terminal emitters exhibit negligible external quantum efficiency drops compared with non-doped devices, enabling a maximum external quantum efficiency of 21.5%. To explain the high efficiency in the absence of high-gap matrices, we turn to transient absorption spectroscopy. It is directly observed that Dexter transfer from a pristine thermally activated delayed fluorescence sensitizer host can be substantially reduced by an encapsulated terminal emitter, opening the door to highly efficient 'matrix-free' blue hyperfluorescence.

Synthesis and intramolecular singlet fission properties of ortho-phenylene linked oligomers of diphenylhexatriene.

In molecular dimers that undergo intramolecular singlet fission (iSF), efficient iSF is typically accompanied by triplet pair annihilation at rates which prohibit effective triplet harvesting. Collisional triplet pair separation and intramolecular separation by hopping to additional sites in extended oligomers are both strategies that have been reported to be effective for acene based iSF materials in the literature. Herein, a family of highly soluble diphenylhexatriene (DPH) oligomers were synthesized and investigated using transient absorption spectroscopy to determine whether these approaches can be applied to the non-acene singlet fission chromophore, DPH. While iSF proceeds rapidly for all three new materials, neither concentration nor oligomer size result in significantly enhanced triplet pair lifetime relative to the dilute dimer case. These null results indicate the fallibility of the collisional separation and oligomerisation strategies.

EGFR-targeted semiconducting polymer nanoparticles for photoacoustic imaging.

Semiconducting polymer nanoparticles (SPN), formulated from organic semiconducting polymers and lipids, show promise as exogenous contrast agents for photoacoustic imaging (PAI). To fully realise the potential of this class of nanoparticles for imaging and therapeutic applications, a broad range of active targeting strategies, where ligands specific to receptors on the target cells are displayed on the SPN surface, are urgently needed. In addition, effective strategies for quantifying the level of surface modification are also needed to support development of ligand-targeted SPN. In this paper, we have developed methods to prepare SPN bearing peptides targeted to Epidermal Growth Factor Receptors (EGFR), which are overexpressed at the surface of a wide variety of cancer cell types. In addition to fully characterising these targeted nanoparticles by standard methods (UV-visible, photoacoustic absorption, dynamic light scattering, zeta potential and SEM), we have developed a powerful new NMR method to determine the degree of conjugation and the number of targeting peptides attached to the SPN. Preliminary in vitro experiments with the colorectal cancer cell line LIM1215 indicated that the EGFR-targeting peptide conjugated SPN were either ineffective in delivering the SPN to the cells, or that the targeting peptide itself destabilised the formulation. This in reinforces the need for effective characterisation techniques to measure the surface accessibility of targeting ligands attached to nanoparticles.

Mesitylated trityl radicals, a platform for doublet emission: symmetry breaking, charge-transfer states and conjugated polymers.

Neutral π-radicals have potential for use as light emitters in optoelectronic devices due to the absence of energetically low-lying non-emissive states. Here, we report a defect-free synthetic methodology via mesityl substitution at the para-positions of tris(2,4,6-trichlorophenyl)methyl radical. These materials reveal a number of novel optoelectronic properties. Firstly, mesityl substituted radicals show strongly enhanced photoluminescence arising from symmetry breaking in the excited state. Secondly, photoexcitation of thin films of 8 wt% radical in 4,4'-bis(carbazol-9-yl)-1,1'-biphenyl host matrix produces long lived (in the order of microseconds) intermolecular charge transfer states, following hole transfer to the host, that can show unexpectedly efficient red-shifted emission. Thirdly, covalent attachment of carbazole into the mesitylated radical gives very high photoluminescence yield of 93% in 4,4'-bis(carbazol-9-yl)-1,1'-biphenyl films and light-emitting diodes with maximum external quantum efficiency of 28% at a wavelength of 689 nm. Fourthly, a main-chain copolymer of the mesitylated radical and 9,9-dioctyl-9H-fluorene shows red-shifted emission beyond 800 nm.

Re-Thinking Dimer Design Principles with Indolonaphthyridine Intramolecular Singlet Fission.

Singlet fission is a phenomenon that could significantly improve the efficiency of photovoltaic devices. Indolonaphthyridine thiophene (INDT) is a photostable singlet fission material that could potentially be utilised in singlet fission-based photovoltaic devices. This study investigates the intramolecular singlet fission (i-SF) mechanism of INDT dimers linked via para-phenyl, meta-phenyl and fluorene bridging groups. Using ultra-fast spectroscopy the highest rate of singlet fission is found in the para-phenyl linked dimer. Quantum calculations show the para-phenyl linker encourages enhanced monomer electronic coupling. Increased rates of singlet fission were also observed in the higher polarity o-dichlorobenzene, relative to toluene, indicating that charge-transfer states have a role in mediating the process. The mechanistic picture of polarisable singlet fission materials, such as INDT, extends beyond the traditional mechanistic landscape.

Aza-Cibalackrot: Turning on Singlet Fission Through Crystal Engineering.

Singlet fission is a photophysical process that provides a pathway for more efficient harvesting of solar energy in photovoltaic devices. The design of singlet fission candidates is non-trivial and requires careful optimization of two key criteria: (1) correct energetic alignment and (2) appropriate intermolecular coupling. Meanwhile, this optimization must not come at the cost of molecular stability or feasibility for device applications. Cibalackrot is a historic and stable organic dye which, although it has been suggested to have ideal energetics, does not undergo singlet fission due to large interchromophore distances, as suggested by single crystal analysis. Thus, while the energetic alignment is satisfactory, the molecule does not have the desired intermolecular coupling. Herein, we improve this characteristic through molecular engineering with the first synthesis of an aza-cibalackrot and show, using ultrafast transient spectroscopy, that singlet fission is successfully "turned on."

Generating Long-Lived Triplet Excited States in Narrow Bandgap Conjugated Polymers.

Narrow bandgap conjugated polymers are a heavily studied class of organic semiconductors, but their excited states usually have a very short lifetime, limiting their scope for applications. One approach to overcome the short lifetime is to populate long-lived triplet states for which relaxation to the ground state is forbidden. However, the triplet lifetime of narrow bandgap polymer films is typically limited to a few microseconds. Here, we investigated the effect of film morphology on triplet dynamics in red-emitting conjugated polymers based on the classic benzodithiophene monomer unit with the solubilizing alkyl side chains C16 and C2C6 and then used Pd porphyrin sensitization as a further strategy to change the triplet dynamics. Using transient absorption spectroscopy, we demonstrated a 0.45 ms triplet lifetime for the more crystalline nonsensitized polymer C2C6, 2-3 orders of magnitude longer than typically reported, while the amorphous C16 had only a 5 µs lifetime. The increase is partly due to delaying bimolecular electron-hole recombination in the more crystalline C2C6, where a higher energy barrier for charge recombination is expected. A triplet lifetime of 0.4 ms was also achieved by covalently incorporating 5% of Pd porphyrin into the C16 polymer, which introduced extra energy transfer steps between the polymer and porphyrin that delayed triplet dynamics and increased the polymer triplet yield by 7.9 times. This work demonstrates two synthetic approaches to generate the longest-lived triplet excited states in narrow bandgap conjugated polymers, which is of necessity in a wide range of fields that range from organic electronics to sensors and bioapplications.

Soluble Diphenylhexatriene Dimers for Intramolecular Singlet Fission with High Triplet Energy.

Intramolecular singlet fission (iSF) facilitates single-molecule exciton multiplication, converting an excited singlet state to a pair of triplet states within a single molecule. A critical parameter in determining the feasibility of SF-enhanced photovoltaic designs is the triplet energy; many existing iSF materials have triplet energies too low for efficient transfer to silicon via a photon multiplier scheme. In this work, a series of six novel dimers based upon the high-triplet-energy, SF-active chromophore, 1,6-diphenyl-1,3,5-hexatriene (DPH) [E(T1) ∼ 1.5 eV], were designed, synthesized, and characterized. Transient absorption spectroscopy and fluorescence lifetime studies reveal that five of the dimers display iSF activity, with time constants for singlet fission varying between 7 ± 2 ps and 2.2 ± 0.2 ns and a high triplet yield of 163 ± 63% in the best-performing dimer. A strong dependence of the rate of fission on the coupling geometry is demonstrated. For optimized iSF behavior, close spatial proximity and minimal through-bond communication are found to be crucial for balancing the rate of SF against the reverse recombination process.

Triplet transfer from PbS quantum dots to tetracene ligands: is faster always better?

Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications.

Quantitative Singlet Fission in Solution-Processable Dithienohexatrienes.

Singlet fission (SF) is a promising strategy to overcome thermalization losses and enhance the efficiency of single junction photovoltaics (PVs). The development of this field has been strongly material-limited, with a paucity of materials able to undergo SF. Rarer still are examples that can produce excitons of sufficient energy to be coupled to silicon PVs (>1.1 eV). Herein, we examine a series of a short-chain polyene, dithienohexatriene (DTH), with tailored material properties and triplet (T1) energy levels greater than 1.1 eV. We find that these highly soluble materials can be easily spin-cast to create thin films of high crystallinity that exhibit ultrafast singlet fission with near perfect triplet yields of up to 192%. We believe that these materials are the first solution-processable singlet fission materials with quantitative triplet formation and energy levels appropriate for use in conjunction with silicon PVs.

Effects of Molecular Encapsulation on the Photophysical and Charge Transport Properties of a Naphthalene Diimide Bithiophene Copolymer.

Engineering the molecular structure of conjugated polymers is key to advancing the field of organic electronics. In this work, we synthesized a molecularly encapsulated version of the naphthalene diimide bithiophene copolymer PNDIT2, which is among the most popular high charge mobility organic semiconductors in n-type field-effect transistors and non-fullerene acceptors in organic photovoltaic blends. The encapsulating macrocycles shield the bithiophene units while leaving the naphthalene diimide units available for intermolecular interactions. With respect to PNDIT2, the encapsulated counterpart displays an increased backbone planarity. Molecular encapsulation prevents preaggregation of the polymer chains in common organic solvents, while it permits π-stacking in the solid state and promotes thin film crystallinity through an intermolecular-lock mechanism. Consequently, n-type semiconducting behavior is retained in field-effect transistors, although charge mobility is lower than in PNDIT2 due to the absence of the fibrillar microstructure that originates from preaggregation in solution. Hence, molecularly encapsulating conjugated polymers represent a promising chemical strategy to tune the molecular interaction in solution and the backbone conformation and to consequently control the nanomorphology of casted films without altering the electronic structure of the core polymer.

Molecular Encapsulation of Naphthalene Diimide (NDI) Based π-Conjugated Polymers: A Tool for Understanding Photoluminescence.

Conjugated polymers are an important class of chromophores for optoelectronic devices. Understanding and controlling their excited state properties, in particular, radiative and non-radiative recombination processes are among the greatest challenges that must be overcome. We report the synthesis and characterization of a molecularly encapsulated naphthalene diimide-based polymer, one of the most successfully used motifs, and explore its structural and optical properties. The molecular encapsulation enables a detailed understanding of the effect of interpolymer interactions. We reveal that the non-encapsulated analogue P(NDI-2OD-T) undergoes aggregation enhanced emission; an effect that is suppressed upon encapsulation due to an increasing π-interchain stacking distance. This suggests that decreasing π-stacking distances may be an attractive method to enhance the radiative properties of conjugated polymers in contrast to the current paradigm where it is viewed as a source of optical quenching.

Transition-Metal-Free Homopolymerization of Pyrrolo[2,3-d:5,4-d']bisthiazoles via Nucleophilic Aromatic Substitution.

Novel methods to synthesize electron-deficient π-conjugated polymers utilizing transition-metal-free coupling reactions for the use of nonfunctionalized monomers are attractive due to their improved atom economy and environmental prospective. Herein we describe the use of iPrMgCl·LiCl complex to afford thiazole-based conjugated polymers in the absence of any transition metal catalyst, that enables access to well-defined polymers with good molecular weights. The mechanistically distinct polymerizations proceeded via nucleophilic aromatic substitution (SNAr) reaction supported by density functional theory (DFT) calculations. This work demonstrates the first example of fully conjugated thiazole-based aromatic homopolymers without the need of any transition metal catalyst.