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

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

Elucidating the non-radiative losses encountered in intramolecular charge transfer compounds with benzodithiophene-4,8-dione acceptors

A new yellow-emitting quadrupolar donor-π-acceptor-π-donor (D-π-A-π-D) molecule compound has been synthesised featuring benzo-[1,2-c:4,5-c′]dithiophene-4,8-dione as the acceptor. This molecule was prepared for the purpose of elucidating the origins of the very low photoluminescence quantum yield encountered in its thermally activated delayed fluorescent (TADF) red-emitting isomer which used benzo-[1,2-b:4,5-b′]dithiophene-4,8-dione as the acceptor. The molecule was designed to circumvent the energy gap law, by having a wider HOMO-LUMO gap, while retaining a comparable singlet-triplet gap but ultimately demonstrates even weaker photoluminescence than the red isomer. It shows extremely fast intersystem crossing followed by rapid non-radiative decay and no observable TADF. The electronic structure of this new molecule has been studied using cyclic voltammatery alongside steady-state and transient optical spectroscopy, with observations underpinned by computational insights. To identify whether the observations made from the experimental results might be general properties of benzodithiophene-4,8-dione containing emitters, a computational study is extended to the four isomers of benzodithiophene-4,8-dione in comparison with 9,10-anthraquinone. The results suggest that the singlet and triplet manifolds of these systems are strongly coupled via spin-orbit interactions, and explain how the relative electron-accepting strength of these quinones arises from an interplay between the resonance gains or losses of the central benzene and fused thiophene rings upon photoexcitation. This provides valuable insights into the design principles required for efficient organic light-emitting materials.</p

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

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

Efficient near-infrared organic light-emitting diodes with emission from spin doublet excitons

The development of luminescent organic radicals has resulted in materials with excellent optical properties for near-infrared (NIR) emission. Applications of light generation in this range span from bioimaging to surveillance. Whilst the unpaired electron arrangements of radicals enable efficient radiative transitions within the doublet-spin manifold in organic light-emitting diodes (OLEDs), their performance is limited by non-radiative pathways introduced in electroluminescence. Here, we present a host:guest design for OLEDs that exploits energy transfer with demonstration of up to 9.6% external quantum efficiency (EQE) for 800 nm emission. The tris(2,4,6-trichlorophenyl)methyl-triphenylamine (TTM-TPA) radical guest is energy-matched to the triplet state in a charge-transporting anthracene-derivative host. We show from optical spectroscopy and quantum-chemical modelling that reversible host-guest triplet-doublet energy transfer allows efficient harvesting of host triplet excitons

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.Includes EPSRC

Reversible spin-optical interface in luminescent organic radicals

Molecules present a versatile platform for quantum information science, and are candidates for sensing and computation applications. Robust spin-optical interfaces are key to harnessing the quantum resources of materials. To date, carbon-based candidates have been non-luminescent, which prevents optical read-out. Here we report the first organic molecules displaying both efficient luminescence and near-unity generation yield of high-spin multiplicity excited states. This is achieved by designing an energy resonance between emissive doublet and triplet levels, here on covalently coupled tris(2,4,6-trichlorophenyl) methyl-carbazole radicals (TTM-1Cz) and anthracene. We observe the doublet photoexcitation delocalise onto the linked acene within a few picoseconds and subsequently evolve to a pure high spin state (quartet for monoradicals, 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 read-out enabled by 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 show strong spin correlation. Our approach simultaneously supports a high efficiency of initialisation, spin manipulations and light-based read-out at room temperature. The integration of luminescence and high-spin states creates an organic materials platform for emerging quantum technologies

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

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

Abstract: 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