Fast transfer of triplet to doublet excitons from organometallic host to organic radical semiconductors.

Spin triplet exciton formation sets limits on technologies using organic semiconductors that are confined to singlet-triplet photophysics. In contrast, excitations in the spin doublet manifold in organic radical semiconductors can show efficient luminescence. Here we explore the dynamics of the spin allowed process of intermolecular energy transfer from triplet to doublet excitons. We employ a carbene-metal-amide (CMA-CF3) as a model triplet donor host, since following photoexcitation it undergoes extremely fast intersystem crossing to set up a population of triplet excitons within 4 ps. This enables a foundational study for tracking energy transfer from triplets to a model radical semiconductor, TTM-3PCz. Over 74% of all radical luminescence originates from the triplet channel in this system under photoexcitation. We find that intermolecular triplet-to-doublet energy transfer can occur directly and rapidly, with 12% of triplet excitons transferring already on sub-ns timescales. This enhanced triplet harvesting mechanism is utilised in efficient near-infrared organic light-emitting diodes, which can be extended to other opto-electronic and -spintronic technologies by radical-based spin control in molecular semiconductors. This article is protected by copyright. All rights reserved.

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.

Peri-Alkylated Terrylenes and Ternaphthalenes Building-Blocks Towards Multi-Edge Nanographenes.

Since its first synthesis by Clar in 1948, terrylene - a fully connected ternaphthalene oligomer via naphthalene's peri-positions - has gained special focus within the rylene family, drawing interest for its unique chemical, structural, optoelectronic and single photon emission properties. In this study, we introduce a novel synthetic pathway that enhances the solubility of terrylene derivatives through complete peri-alkylation, while also facilitating extensions at the bay-positions. This approach not only broadens the scope of terrylene's chemical versatility but also opens new avenues for developing solution processable novel multi-edge nanographenes and tailoring electronic energy levels through topological edge structures. Our findings include a comprehensive structural and spectroscopic characterization along with transient absorption spectroscopy and photophysics of both the synthesized peri-alkylated terrylene and its phenylene-fused derivative.

Radical Spin Polarization and Magnetosensitivity from Reversible Energy Transfer.

Molecular spins provide potential building units for future quantum information science and spintronic technologies. In particular, doublet (S = 1/2) and triplet (S = 1) molecular spin states have the potential for excellent optical and spin properties for these applications if useful photon-spin mechanisms at room temperature can be devised. Here we explore the potential of exploiting reversible energy transfer between triplet and doublet states to establish magnetosensitive luminescence and spin polarization. We investigate the dependence of the photon-spin mechanism on the magnitude and sign of the exchange interaction between the doublet and triplet spin components in amorphous and crystalline model systems. The design of a magnetic field inclination sensor is proposed from understanding the required "structure" (spin interactions) to "function" (magnetosensitivity).

Efficient and Bright Organic Radical Light-Emitting Diodes with Low Efficiency Roll-Off.

Organic radicals have been of interest due to their potential to replace nonradical-based organic emitters, especially for deep-red/near-infrared (NIR) electroluminescence (EL), based on the spin-allowed doublet fluorescence. However, the performance of the radical-based EL devices is limited by low carrier mobility which causes a large efficiency roll-off at high current densities. Here, highly efficient and bright doublet EL devices are reported by combining a thermally activated delayed fluorescence (TADF) host that supports both electron and hole transport and a tris(2,4,6-trichlorophenyl)methyl-based radical emitter. Steady-state and transient photophysical studies reveal the optical signatures of doublet luminescence mechanisms arising from both host and guest photoexcitation. The host system presented here allows balanced hole and electron currents, and a high maximum external quantum efficiency (EQE) of 17.4% at 707 nm peak emission with substantially improved efficiency roll-off is reported: over 70% of the maximum EQE (12.2%) is recorded at 10 mA cm-2 , and even at 100 mA cm-2 , nearly 50% of the maximum EQE (8.4%) is maintained. This is an important step in the practical application of organic radicals to NIR light-emitting devices.

Reversible spin-optical interface in luminescent organic radicals.

Molecules present a versatile platform for quantum information science1,2 and are candidates for sensing and computation applications3,4. Robust spin-optical interfaces are key to harnessing the quantum resources of materials5. To date, carbon-based candidates have been non-luminescent6,7, which prevents optical readout via emission. Here we report organic molecules showing both efficient luminescence and near-unity generation yield of excited states with spin multiplicity S > 1. This was achieved by designing an energy resonance between emissive doublet and triplet levels, here on covalently coupled tris(2,4,6-trichlorophenyl) methyl-carbazole radicals and anthracene. We observed that the doublet photoexcitation delocalized onto the linked acene within a few picoseconds and subsequently evolved to a pure high-spin state (quartet for monoradical, quintet for biradical) of mixed radical-triplet character near 1.8 eV. These high-spin states are coherently addressable with microwaves even at 295 K, with optical readout enabled by reverse intersystem crossing to emissive states. Furthermore, for the biradical, on return to the ground state the previously uncorrelated radical spins either side of the anthracene shows strong spin correlation. Our approach simultaneously supports a high efficiency of initialization, spin manipulations and light-based readout at room temperature. The integration of luminescence and high-spin states creates an organic materials platform for emerging quantum technologies.

Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters.

Thermally activated delayed fluorescence enables organic semiconductors with charge transfer-type excitons to convert dark triplet states into bright singlets via reverse intersystem crossing. However, thus far, the contribution from the dielectric environment has received insufficient attention. Here we study the role of the dielectric environment in a range of thermally activated delayed fluorescence materials with varying changes in dipole moment upon optical excitation. In dipolar emitters, we observe how environmental reorganization after excitation triggers the full charge transfer exciton formation, minimizing the singlet-triplet energy gap, with the emergence of two (reactant-inactive) modes acting as a vibrational fingerprint of the charge transfer product. In contrast, the dielectric environment plays a smaller role in less dipolar materials. The analysis of energy-time trajectories and their free-energy functions reveals that the dielectric environment substantially reduces the activation energy for reverse intersystem crossing in dipolar thermally activated delayed fluorescence emitters, increasing the reverse intersystem crossing rate by three orders of magnitude versus the isolated molecule.

Singlet and triplet to doublet energy transfer: improving organic light-emitting diodes with radicals.

Organic light-emitting diodes (OLEDs) must be engineered to circumvent the efficiency limit imposed by the 3:1 ratio of triplet to singlet exciton formation following electron-hole capture. Here we show the spin nature of luminescent radicals such as TTM-3PCz allows direct energy harvesting from both singlet and triplet excitons through energy transfer, with subsequent rapid and efficient light emission from the doublet excitons. This is demonstrated with a model Thermally-Activated Delayed Fluorescence (TADF) organic semiconductor, 4CzIPN, where reverse intersystem crossing from triplets is characteristically slow (50% emission by 1 µs). The radical:TADF combination shows much faster emission via the doublet channel (80% emission by 100 ns) than the comparable TADF-only system, and sustains higher electroluminescent efficiency with increasing current density than a radical-only device. By unlocking energy transfer channels between singlet, triplet and doublet excitons, further technology opportunities are enabled for optoelectronics using organic radicals.

Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors.

Engineering a low singlet-triplet energy gap (ΔEST) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 × 105 cm-1) and a relatively large ΔEST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 µs), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a ~24 ns timescale and have an average electron-hole separation of ≥1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low ΔEST in organic DF emitters.

Electron spin resonance resolves intermediate triplet states in delayed fluorescence.

Molecular organic fluorophores are currently used in organic light-emitting diodes, though non-emissive triplet excitons generated in devices incorporating conventional fluorophores limit the efficiency. This limit can be overcome in materials that have intramolecular charge-transfer excitonic states and associated small singlet-triplet energy separations; triplets can then be converted to emissive singlet excitons resulting in efficient delayed fluorescence. However, the mechanistic details of the spin interconversion have not yet been fully resolved. We report transient electron spin resonance studies that allow direct probing of the spin conversion in a series of delayed fluorescence fluorophores with varying energy gaps between local excitation and charge-transfer triplet states. The observation of distinct triplet signals, unusual in transient electron spin resonance, suggests that multiple triplet states mediate the photophysics for efficient light emission in delayed fluorescence emitters. We reveal that as the energy separation between local excitation and charge-transfer triplet states decreases, spin interconversion changes from a direct, singlet-triplet mechanism to an indirect mechanism involving intermediate states.

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers.

Controlling the flow of electrical current at the nanoscale typically requires complex top-down approaches. Here, a bottom-up approach is employed to demonstrate resistive switching within molecular wires that consist of double-helical metallopolymers and are constructed by self-assembly. When the material is exposed to an electric field, it is determined that ≈25% of the copper atoms oxidize from CuI to CuII , without rupture of the polymer chain. The ability to sustain such a high level of oxidation is unprecedented in a copper-based molecule: it is made possible here by the double helix compressing in order to satisfy the new coordination geometry required by CuII . This mixed-valence structure exhibits a 104 -fold increase in conductivity, which is projected to last on the order of years. The increase in conductivity is explained as being promoted by the creation, upon oxidation, of partly filled d z 2 orbitals aligned along the mixed-valence copper array; the long-lasting nature of the change in conductivity is due to the structural rearrangement of the double-helix, which poses an energetic barrier to re-reduction. This work establishes helical metallopolymers as a new platform for controlling currents at the nanoscale.

Understanding the luminescent nature of organic radicals for efficient doublet emitters and pure-red light-emitting diodes.

The doublet-spin nature of radical emitters is advantageous for applications in organic light-emitting diodes, as it avoids the formation of triplet excitons that limit the electroluminescence efficiency of non-radical emitters. However, radicals generally show low optical absorption and photoluminescence yields. Here we explain the poor optical properties of radicals based on alternant hydrocarbons, and establish design rules to increase the absorption and luminescence yields for donor-acceptor-type radicals. We show that non-alternant systems are necessary to lift the degeneracy of the lowest energy orbital excitations; moreover, intensity borrowing from an intense high-lying transition by the low-energy charge-transfer excitation enhances the oscillator strength of the emitter. We apply these rules to design tris(2,4,6-trichlorophenyl)methyl-pyridoindolyl derivatives with a high photoluminescence quantum yield (>90%). Organic light-emitting diodes based on these molecules showed a pure-red emission with an over 12% external quantum efficiency. These insights may be beneficial for the rational design and discovery of highly luminescent doublet emitters.

Perylene-Based Covalent Organic Frameworks for Acid Vapor Sensing.

Traditionally, the properties and functions of covalent organic frameworks (COFs) are defined by their constituting building blocks, while the chemical bonds that connect the individual subunits have not attracted much attention as functional components of the final material. We have developed a new series of dual-pore perylene-based COFs and demonstrated that their imine bonds can be protonated reversibly, causing significant protonation-induced color shifts toward the near-infrared, while the structure and crystallinity of the frameworks are fully retained. Thin films of these COFs are highly sensitive colorimetric acid vapor sensors with a detection limit as low as 35 µg L-1 and a response range of at least 4 orders of magnitude. Since the acidochromism in our COFs is a cooperative phenomenon based on electronically coupled imines, the COFs can be used to determine simultaneously the concentration and protonation strength of nonaqueous acid solutions, in which pH electrodes are not applicable, and to distinguish between different acids. Including the imine bonds as function-determining constituents of the framework provides an additional handle for constructing multifunctional COFs and extending the range of their possible applications.

High stability and luminescence efficiency in donor-acceptor neutral radicals not following the Aufbau principle.

With their unusual electronic structures, organic radical molecules display luminescence properties potentially relevant to lighting applications; yet, their luminescence quantum yield and stability lag behind those of other organic emitters. Here, we designed donor-acceptor neutral radicals based on an electron-poor perchlorotriphenylmethyl or tris(2,4,6-trichlorophenyl)methyl radical moiety combined with different electron-rich groups. Experimental and quantum-chemical studies demonstrate that the molecules do not follow the Aufbau principle: the singly occupied molecular orbital is found to lie below the highest (doubly) occupied molecular orbital. These donor-acceptor radicals have a strong emission yield (up to 54%) and high photostability, with estimated half-lives reaching up to several months under pulsed ultraviolet laser irradiation. Organic light-emitting diodes based on such a radical emitter show deep-red/near-infrared emission with a maximal external quantum efficiency of 5.3%. Our results provide a simple molecular-design strategy for stable, highly luminescent radicals with non-Aufbau electronic structures.

Red-shifted delayed fluorescence at the expense of photoluminescence quantum efficiency - an intramolecular charge-transfer molecule based on a benzodithiophene-4,8-dione acceptor.

Employing the thiophene based quinone, benzo[1,2-b:4,5-b']dithiophene-4,8-dione, as the electron-accepting moiety alongside N-phenylcarbazole donors to produce a donor-π-acceptor-π-donor (D-π-A-π-D) molecule has yielded a new red emitter displaying delayed fluorescence. This new molecule shows strongly (over 100 nm) red-shifted emission when compared to an anthraquinone based analogue. Cyclic voltammetry complemented by computational insights prove that this red-shift is due to the significantly stronger electron-accepting ability of the thiophene quinone compared to anthraquinone. Photophysical and computational studies of this molecule have revealed that while the presence of the thiophene containing acceptor facilitates rapid intersystem crossing which is comparable to anthraquinone analogues, the reverse intersystem crossing rate is slow and non-radiative decay is rapid which we can attribute to low-lying locally excited states. This limits the total photoluminescence quantum efficiency to less than 10% in both solution and the solid state. These results provide a useful example of how very minor structural variations can have a defining impact on the photophysical properties of new molecular materials.

Efficient radical-based light-emitting diodes with doublet emission.

Organic light-emitting diodes (OLEDs)1-5, quantum-dot-based LEDs6-10, perovskite-based LEDs11-13 and micro-LEDs14,15 have been championed to fabricate lightweight and flexible units for next-generation displays and active lighting. Although there are already some high-end commercial products based on OLEDs, costs must decrease whilst maintaining high operational efficiencies for the technology to realise wider impact.  Here we demonstrate efficient action of radical-based OLEDs16, whose emission originates from a spin doublet, rather than a singlet or triplet exciton. While the emission process is still spin-allowed in these OLEDs, the efficiency limitations imposed by triplet excitons are circumvented for doublets. Using a luminescent radical emitter, we demonstrate an OLED with maximum external quantum efficiency of 27 per cent at a wavelength of 710 nanometres-the highest reported value for deep-red and infrared LEDs. For a standard closed-shell organic semiconductor, holes and electrons occupy the highest occupied and lowest unoccupied molecular orbitals (HOMOs and LUMOs), respectively, and recombine to form singlet or triplet excitons. Radical emitters have a singly occupied molecular orbital (SOMO) in the ground state, giving an overall spin-1/2 doublet. If-as expected on energetic grounds-both electrons and holes occupy this SOMO level, recombination returns the system to the ground state, giving no light emission. However, in our very efficient OLEDs, we achieve selective hole injection into the HOMO and electron injection to the SOMO to form the fluorescent doublet excited state with near-unity internal quantum efficiency.

Solvatochromic covalent organic frameworks.

Covalent organic frameworks (COFs) are an emerging class of highly tuneable crystalline, porous materials. Here we report the first COFs that change their electronic structure reversibly depending on the surrounding atmosphere. These COFs can act as solid-state supramolecular solvatochromic sensors that show a strong colour change when exposed to humidity or solvent vapours, dependent on vapour concentration and solvent polarity. The excellent accessibility of the pores in vertically oriented films results in ultrafast response times below 200 ms, outperforming commercially available humidity sensors by more than an order of magnitude. Employing a solvatochromic COF film as a vapour-sensitive light filter, we demonstrate a fast humidity sensor with full reversibility and stability over at least 4000 cycles. Considering their immense chemical diversity and modular design, COFs with fine-tuned solvatochromic properties could broaden the range of possible applications for these materials in sensing and optoelectronics.

Efficient Vacuum-Processed Light-Emitting Diodes Based on Carbene-Metal-Amides.

Efficient vacuum-processed organic light-emitting diodes are fabricated using a carbene-metal-amide material, CMA1. An electroluminescence (EL) external quantum efficiency of 23% is achieved in a host-free emissive layer comprising pure CMA1. Furthermore external quantum efficiencies of up to 26.9% are achieved in host-guest emissive layers. EL spectra are found to depend on both the emissive-layer doping concentration and the choice of host material, enabling tuning of emission color from mid-green (Commission Internationale de l'Éclairage co-ordinates [0.24, 0.46]) to sky blue ([0.22 0.35]) without changing dopant. This tuning is achieved without compromising luminescence efficiency (>80%) while maintaining a short radiative lifetime of triplets (<1 µs).

Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers.

Self-assembled helical polymers hold great promise as new functional materials, where helical handedness controls useful properties such as circularly polarized light emission or electron spin. The technique of subcomponent self-assembly can generate helical polymers from readily prepared monomers. Here we present three distinct strategies for chiral induction in double-helical metallopolymers prepared via subcomponent self-assembly: (1) employing an enantiopure monomer, (2) polymerization in a chiral solvent, (3) using an enantiopure initiating group. Kinetic and thermodynamic models were developed to describe the polymer growth mechanisms and quantify the strength of chiral induction, respectively. We found the degree of chiral induction to vary as a function of polymer length. Ordered, rod-like aggregates more than 70 nm long were also observed in the solid state. Our findings provide a basis to choose the most suitable method of chiral induction based on length, regiochemical, and stereochemical requirements, allowing stereochemical control to be established in easily accessible ways.

Vibrationally Assisted Intersystem Crossing in Benchmark Thermally Activated Delayed Fluorescence Molecules.

Electrically injected charge carriers in organic light-emitting devices (OLEDs) undergo recombination events to form singlet and triplet states in a 1:3 ratio, representing a fundamental hurdle for achieving high quantum efficiency. Dopants based on thermally activated delayed fluorescence (TADF) have emerged as promising candidates for addressing the spin statistics issue in OLEDs. In these materials, reverse singlet-triplet intersystem crossing (rISC) becomes efficient, thereby activating luminescence pathways for weakly emissive triplet states. However, despite a growing consensus that torsional vibrations facilitate spin-orbit-coupling- (SOC-) driven ISC in these molecules, there is a shortage of experimental evidence. We use transient electron spin resonance and theory to show unambiguously that SOC interactions drive spin conversion and that ISC is a dynamic process gated by conformational fluctuations for benchmark carbazolyl-dicyanobenzene TADF emitters.