Excited-State Engineering Enables Efficient Deep-Blue Light-Emitting Diodes Exhibiting BT.2020 Color Gamut.

Organic luminescent materials that exhibit thermally activated delayed fluorescence (TADF) can convert non-emissive triplet excitons into emissive singlet states through a reverse intersystem crossing (RISC) process. Therefore, they have tremendous potential for applications in organic light-emitting diodes (OLEDs). However, with the development of ultra-high definition 4K/8K display technologies, designing efficient deep-blue TADF materials to achieve the Commission Internationale de l'Éclairage (CIE) coordinates fulfilling BT.2020 remains a significant challenge. Here, an effective approach is proposed to design deep-blue TADF molecules based on hybrid long- and short-range charge-transfer by incorporation of multiple donor moieties into organoboron multiple resonance acceptors. The resulting TADF molecule exhibits deep-blue emission at 414 nm with a full width at half maximum (FWHM) of 29 nm, together with a thousand-fold increase in RISC rate. OLEDs based on the champion material achieve a record maximum external quantum efficiency (EQE) of 22.8% with CIE coordinates of (0.163, 0.046), approaching the coordinates of the BT.2020 blue standard. Moreover, TADF-assisted fluorescence devices employing the designed material as a sensitizer exhibit an exceptional EQE of 33.1%. This work thus provides a blueprint for future development of efficient deep-blue TADF emitters, representing an important milestone towards meeting the blue color gamut standard of BT.2020.

A Heterometallic Porphyrin Dimer as a Potential Quantum Gate: Magneto-Structural Correlations and Spin Coherence Properties.

In the development of two-qubit quantum gates, precise control over the intramolecular spin-spin interaction between molecular spin units plays a pivotal role. A weak but measurable exchange coupling is especially important for achieving selective spin addressability that allows controlled manipulation of the computational basis states |00⟩ |01⟩ |10⟩ |11⟩ by microwave pulses. Here, we report the synthesis and Electron Paramagnetic Resonance (EPR) study of a heterometallic meso-meso (m-m) singly-linked VIV O-CuII porphyrin dimer. X-band continuous wave EPR measurements in frozen solutions suggest a ferromagnetic exchange coupling of ca. 8 ⋅ 10-3  cm-1 . This estimation is supported by Density Functional Theory calculations, which also allow disentangling the ferro- and antiferromagnetic contributions to the exchange. Pulsed EPR experiments show that the dimer maintains relaxation times similar to the monometallic CuII porphyrins. The addressability of the two individual spins is made possible by the different g-tensors of VIV and CuII -ions, in contrast to homometallic dimers where tilting of the porphyrin planes plays a key role. Therefore, single-spin addressability in the heterometallic dimer can be maintained even with small tilting angles, as expected when deposited on surface, unlocking the full potential of molecular quantum gates for practical applications.

Challenges in the Direct Detection of Chirality-induced Spin Selectivity: Investigation of Foldamer-based Donor-acceptor Dyads.

Over the past two decades, the chirality-induced spin selectivity (CISS) effect was reported in several experiments disclosing a unique connection between chirality and electron spin. Recent theoretical works highlighted time-resolved Electron Paramagnetic Resonance (trEPR) as a powerful tool to directly detect the spin polarization resulting from CISS. Here, we report a first attempt to detect CISS at the molecular level by linking the pyrene electron donor to the fullerene acceptor with chiral peptide bridges of different length and electric dipole moment. The dyads are investigated by an array of techniques, including cyclic voltammetry, steady-state and transient optical spectroscopies, and trEPR. Despite the promising energy alignment of the electronic levels, our multi-technique analysis reveals no evidence of electron transfer (ET), highlighting the challenges of spectroscopic detection of CISS. However, the analysis allows the formulation of guidelines for the design of chiral organic model systems suitable to directly probe CISS-polarized ET.

Chirality-Induced Spin Selectivity: An Enabling Technology for Quantum Applications.

Molecular spins are promising building blocks of future quantum technologies thanks to the unparalleled flexibility provided by chemistry, which allows the design of complex structures targeted for specific applications. However, their weak interaction with external stimuli makes it difficult to access their state at the single-molecule level, a fundamental tool for their use, for example, in quantum computing and sensing. Here, an innovative solution exploiting the interplay between chirality and magnetism using the chirality-induced spin selectivity effect on electron transfer processes is foreseen. It is envisioned to use a spin-to-charge conversion mechanism that can be realized by connecting a molecular spin qubit to a dyad where an electron donor and an electron acceptor are linked by a chiral bridge. By numerical simulations based on realistic parameters, it is shown that the chirality-induced spin selectivity effect could enable initialization, manipulation, and single-spin readout of molecular qubits and qudits even at relatively high temperatures.

Highly Charged Ru(II) Polypyridyl Complexes as Photosensitizer Agents in Photodynamic Therapy of Epithelial Ovarian Cancer Cells.

Ovarian cancer recurrence is frequent and associated with chemoresistance, leading to extremely poor prognosis. Herein, we explored the potential anti-cancer effect of a series of highly charged Ru(II)-polypyridyl complexes as photosensitizers in photodynamic therapy (PDT), which were able to efficiently sensitize the formation of singlet oxygen upon irradiation (Ru12+ and Ru22+) and to produce reactive oxygen species (ROS) in their corresponding dinuclear metal complexes with the Fenton active Cu(II) ion/s ([CuRu1]4+ and [Cu2Ru2]6+). Their cytotoxic and anti-tumor effects were evaluated on human ovarian cancer A2780 cells both in the absence or presence of photoirradiation, respectively. All the compounds tested were well tolerated under dark conditions, whereas they switched to exert anti-tumor activity following photoirradiation. The specific effect was mediated by the onset of programed cell death, but only in the case of Ru12+ and Ru22+ was preceded by the loss of mitochondrial membrane potential soon after photoactivation and ROS production, thus supporting the occurrence of apoptosis via type II photochemical reactions. Thus, Ru(II)-polypyridyl-based photosensitizers represent challenging tools to be further investigated in the identification of new therapeutic approaches to overcome the innate chemoresistance to platinum derivatives of some ovarian epithelial cancers and to find innovative drugs for recurrent ovarian cancer.

Direct detection of spin polarization in photoinduced charge transfer through a chiral bridge.

It is well assessed that the charge transport through a chiral potential barrier can result in spin-polarized charges. The possibility of driving this process through visible photons holds tremendous potential for several aspects of quantum information science, e.g., the optical control and readout of qubits. In this context, the direct observation of this phenomenon via spin-sensitive spectroscopies is of utmost importance to establish future guidelines to control photo-driven spin selectivity in chiral structures. Here, we provide direct proof that time-resolved electron paramagnetic resonance (EPR) can be used to detect long-lived spin polarization generated by photoinduced charge transfer through a chiral bridge. We propose a system comprising CdSe quantum dots (QDs), as a donor, and C60, as an acceptor, covalently linked through a saturated oligopeptide helical bridge (χ) with a rigid structure of ∼10 Å. Time-resolved EPR spectroscopy shows that the charge transfer in our system results in a C60 radical anion, whose spin polarization maximum is observed at longer times with respect to that of the photogenerated C60 triplet state. Notably, the theoretical modelling of the EPR spectra reveals that the observed features may be compatible with chirality-induced spin selectivity, but the electronic features of the QD do not allow the unambiguous identification of the CISS effect. Nevertheless, we identify which parameters need optimization for unambiguous detection and quantification of the phenomenon. This work lays the basis for the optical generation and direct manipulation of spin polarization induced by chirality.

Nitrogen-Doped Zinc Oxide for Photo-Driven Molecular Hydrogen Production.

Due to its thermal stability, conductivity, high exciton binding energy and high electron mobility, zinc oxide is one of the most studied semiconductors in the field of photocatalysis. However, the wide bandgap requires the use of UV photons to harness its potential. A convenient way to appease such a limitation is the doping of the lattice with foreign atoms which, in turn, introduce localized states (defects) within the bandgap. Such localized states make the material optically active in the visible range and reduce the energy required to initiate photo-driven charge separation events. In this work, we employed a green synthetic procedure to achieve a high level of doping and have demonstrated how the thermal treatment during synthesis is crucial to select specific the microscopic (molecular) nature of the defect and, ultimately, the type of chemistry (reduction versus oxidation) that the material is able to perform. We found that low-temperature treatments produce material with higher efficiency in the water photosplitting reaction. This constitutes a further step in the establishment of N-doped ZnO as a photocatalyst for artificial photosynthesis.

An exchange coupled meso-meso linked vanadyl porphyrin dimer for quantum information processing.

We report here the synthesis of a new meso-meso (m-m) singly linked vanadyl-porphyrin dimer that crystallizes in two different pseudo-polymorphs. The single crystal continuous-wave electron paramagnetic resonance investigation evidences a small but crucial isotropic exchange interaction, J, between the two tilted, and thus distinguishable, spin centers of the order of 10-2 cm-1. The experimental and DFT studies evidence a correlation between J values and porphyrin plane tilting angle and distortion. Pulsed EPR analysis shows that the two vanadyl dimers maintain the coherence time of the monomer. With the obtained spin Hamiltonian parameters, we identify suitable transitions that could be used as computational basis states. Our results, coupled with the evaporability of porphyrin systems, establish this class of dimers as extremely promising for quantum information processing applications.

Correction: An exchange coupled meso-meso linked vanadyl porphyrin dimer for quantum information processing.

[This corrects the article DOI: 10.1039/D2SC04969D.].

The role of charge recombination to triplet excitons in organic solar cells.

The use of non-fullerene acceptors (NFAs) in organic solar cells has led to power conversion efficiencies as high as 18%1. However, organic solar cells are still less efficient than inorganic solar cells, which typically have power conversion efficiencies of more than 20%2. A key reason for this difference is that organic solar cells have low open-circuit voltages relative to their optical bandgaps3, owing to non-radiative recombination4. For organic solar cells to compete with inorganic solar cells in terms of efficiency, non-radiative loss pathways must be identified and suppressed. Here we show that in most organic solar cells that use NFAs, the majority of charge recombination under open-circuit conditions proceeds via the formation of non-emissive NFA triplet excitons; in the benchmark PM6:Y6 blend5, this fraction reaches 90%, reducing the open-circuit voltage by 60 mV. We prevent recombination via this non-radiative channel by engineering substantial hybridization between the NFA triplet excitons and the spin-triplet charge-transfer excitons. Modelling suggests that the rate of back charge transfer from spin-triplet charge-transfer excitons to molecular triplet excitons may be reduced by an order of magnitude, enabling re-dissociation of the spin-triplet charge-transfer exciton. We demonstrate NFA systems in which the formation of triplet excitons is suppressed. This work thus provides a design pathway for organic solar cells with power conversion efficiencies of 20% or more.

The role of spin in the degradation of organic photovoltaics.

Stability is now a critical factor in the commercialization of organic photovoltaic (OPV) devices. Both extrinsic stability to oxygen and water and intrinsic stability to light and heat in inert conditions must be achieved. Triplet states are known to be problematic in both cases, leading to singlet oxygen production or fullerene dimerization. The latter is thought to proceed from unquenched singlet excitons that have undergone intersystem crossing (ISC). Instead, we show that in bulk heterojunction (BHJ) solar cells the photo-degradation of C60 via photo-oligomerization occurs primarily via back-hole transfer (BHT) from a charge-transfer state to a C60 excited triplet state. We demonstrate this to be the principal pathway from a combination of steady-state optoelectronic measurements, time-resolved electron paramagnetic resonance, and temperature-dependent transient absorption spectroscopy on model systems. BHT is a much more serious concern than ISC because it cannot be mitigated by improved exciton quenching, obtained for example by a finer BHJ morphology. As BHT is not specific to fullerenes, our results suggest that the role of electron and hole back transfer in the degradation of BHJs should also be carefully considered when designing stable OPV devices.

Controlling energy levels and Fermi level en route to fully tailored energetics in organic semiconductors.

Simultaneous control over both the energy levels and Fermi level, a key breakthrough for inorganic electronics, has yet to be shown for organic semiconductors. Here, energy level tuning and molecular doping are combined to demonstrate controlled shifts in ionisation potential and Fermi level of an organic thin film. This is achieved by p-doping a blend of two host molecules, zinc phthalocyanine and its eight-times fluorinated derivative, with tunable energy levels based on mixing ratio. The doping efficiency is found to depend on host mixing ratio, which is explained using a statistical model that includes both shifts of the host's ionisation potentials and, importantly, the electron affinity of the dopant. Therefore, the energy level tuning effect has a crucial impact on the molecular doping process. The practice of comparing host and dopant energy levels must consider the long-range electrostatic shifts to consistently explain the doping mechanism in organic semiconductors.

Engineering interactions in QDs-PCBM blends: a surface chemistry approach.

Here we present a comprehensive study on the photophysics of QDs-fullerene blends, aiming to elucidate the impact of ligands on the extraction of carriers from QDs. We investigated how three different ligands (oleylamine, octadecanethiol and propanethiol) influence the dynamics of charge generation, separation, and recombination in blends of CdSe/CdS core/shell QDs and PCBM. We accessed each relevant process directly by combining the results from both optical and magnetic spectroscopies. Transient absorption measurements revealed a faster interaction dynamics in thiol-capped ligands. Through phenomenological modeling of the interaction processes, i.e., energy transfer and electron transfer, we estimated the suppression of exciton migration and the enhancement of electron transfer processes when alkyl-thiols are employed as ligands. Contextually, we report the profound impact of the ligands' alkyl chain length, leading to strengthened interactions with PCBM acceptors. Quantitatively, we measured a 10-fold increase in the electron transfer rate when oleylamine ligands were exchanged with propanethiol ligands. EPR spectroscopy gave access to subtle details regarding both the enhanced charge generation and lower binding energy of charge-transfer states in blends compared to PCBM alone. Moreover, through pulsed EPR techniques, we inferred the localization of deep electron traps in localized sites close to QDs in the blends. Therefore, our thorough characterization evidenced the essential role of ligands in determining QD interactions. We believe that these discoveries will contribute to the efficient incorporation of QDs in existing organic PV technologies.

Hybrid Organic/Inorganic Perovskite-Polymer Nanocomposites: Toward the Enhancement of Structural and Electrical Properties.

Hybrid organic/inorganic perovskite nanoparticles (NPs) have garnered remarkable research attention because of their promising photophysical properties. New and interesting properties emerge after combining perovskite NPs with semiconducting materials. Here, we report the synthesis and investigation of a composite material obtained by mixing CH3NH3PbBr3 nanocrystals with the semiconducting polymer poly(3-hexylthiophene) (P3HT). By the combination of structural techniques and optical and magnetic spectroscopies we observed multiple effects of the perovskite NPs on the P3HT: (i) an enlargement of P3HT crystalline domains, (ii) a strong p-doping of the P3HT, and (iii) an enhancement of interchain order typical of H-aggregates. These observations open a new avenue toward innovative perovskite NP-based applications.

Spectroscopic Insights into Carbon Dot Systems.

The controversial nature of the fluorescent properties of carbon dots (CDs), ascribed either to surface states or to small molecules adsorbed onto the carbon nanostructures, is an unresolved issue. To date, an accurate picture of CDs and an exhaustive structure-property correlation are still lacking. Using two unconventional spectroscopic techniques, fluorescence correlation spectroscopy (FCS) and time-resolved electron paramagnetic resonance (TREPR), we contribute to fill this gap. Although electron micrographs indicate the presence of carbon cores, FCS reveals that the emission properties of CDs are based neither on those cores nor on molecular species linked to them, but rather on free molecules. TREPR provides deeper insights into the structure of carbon cores, where C sp2 domains are embedded within C sp3 scaffolds. FCS and TREPR prove to be powerful techniques, characterizing CDs as inherently heterogeneous systems, providing insights into the nature of such systems and paving the way to standardization of these nanomaterials.

Boosting carbon quantum dots/fullerene electron transfer via surface group engineering.

The design of novel nanostructures with tailored opto-electronic properties is a crucial step for third-generation photovoltaics, and the development of cheap and environmentally compatible materials is still a challenge. Carbon quantum dots (CQDs) emerged as promising candidates but usually a low processability and poor electron-donor properties hampered their photovoltaic applications. We tackle these issues through the synthesis and photophysical characterization of N-doped CQDs functionalized with different thiophene-containing groups. Functionalization was aimed at enhancing the electron donating properties of the carbon dots and improving the solubility in nonpolar solvents. The increased solubility in organic solvents allowed us to investigate the photoinduced interactions of the functionalized carbon dots with the fullerene derivative PCBM in solution and in solid blends. The investigation was carried out by cyclic voltammetry, photoluminescence spectroscopy and electron paramagnetic resonance (EPR). The remarkable oxidation potential shift of the functionalized carbon dots with respect to the pristine materials and the HOMO-LUMO energies strongly suggest them as good electron donors towards PCBM. The electron transfer process between CQDs and PCBM resulted in efficient fluorescence quenching in solution and in total quenching in solid blends. By using EPR spectroscopy in the solid blends, we demonstrated the efficient electron transfer by observing the photoinduced formation of a PCBM radical anion in the presence of functionalized CQDs. Time-resolved EPR allowed us to identify differences in the charge transport efficiency for different CQD:PCBM blends. The enhanced processability of CQDs with PCBM and the promising charge-generation and separation properties pave the way to the development of "all-carbon" photovoltaic devices.

Synthesis and photochemical applications of processable polymers enclosing photoluminescent carbon quantum dots.

Herein, we propose convenient routes to produce hybrid-polymers that covalently enclosed, or confined, N-doped carbon quantum dots (CQDs). We focus our attention on polyamide, polyurea-urethane, polyester, and polymethylmetacrylate polymers, some of the most common resources used to create everyday materials. These hybrid materials can be easily prepared and processed to obtain macroscopic objects of different shapes, i.e., fibers, transparent sheets, and bulky forms, where the characteristic luminescence properties of the native N-doped CQDs are preserved. More importantly we explore the potential use of these hybrid composites to achieve photochemical reactions as those of photoreduction of silver ions to silver nanoparticles (under UV-light), the selective photo-oxidation of benzylalcohol to the benzaldehyde (under vis-light), and the photocatalytic generation of H2 (under UV-light).