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 d2 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

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

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

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

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

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

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

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)