Search Results (31)

This work systematically investigates how different electron-donating groups modulate the photophysical properties and singlet-oxygen quantum yields of donor–acceptor (D–A) distyryl boron-dipyrromethene (BODIPY) photosensitizers, with the donors attached at the para positions of both styryl arms. The study focuses on three compounds that have been previously reported in the literature (M1 with a dimethylacridine donor, M2 with a phenoxazine donor, and M3 with a phenothiazine donor), yet only experimental characterizations are available for them. Using computational chemistry methods, we comprehensively analyzed their geometric configurations, spectral features, spin–orbit coupling (SOC) effects, and electron–hole orbital distributions. The calculated results reveal that M2 possesses the lowest oxidation potential and thus the strongest electron-donating ability among the three donors. Compared with M1 and M3, M2 exhibits larger SOC values, a smaller energy gap between the excited singlet and triplet states, and the highest intersystem crossing (ISC) rate constant. Notably, the energy gaps ΔE (T₁ → S₀) for all three molecules exceed 0.98 eV, which is thermodynamically favorable for sensitizing triplet oxygen to singlet oxygen. Moreover, each of M1–M3 can form dual charge-transfer singlet states, affording two distinct singlet charge-transfer (¹CT) → triplet locally excited (³LE) ISC pathways. This theoretical work demonstrates that dual-donor modification can generate dual charge-transfer states and donor strength serves as an important regulating factor for the intersystem-crossing performance of the three investigated distyryl-BODIPY derivatives. The presence of such dual ISC channels offers a new strategic avenue for the rational design of highly efficient photosensitizers from a theoretical perspective, although further experimental validation in biological systems is required to confirm their therapeutic applicability. Full article

Organic light-emitting diodes (OLEDs) have the advantages of high efficiency and high color purity, which gives them great potential and application prospects in the field of display technology, and thus they have been of wide interest for scholars and industry. Due to their nature, when using the first generation of fluorescent materials, only 25% of the excitons are used, while the rest are wasted, meaning the device efficiency does not exceed 25%. The second generation of phosphorescent materials solves this problem by utilizing 25% singlet excitons while utilizing 75% triplet excitons, achieving 100% internal quantum efficiency. Therefore, a third generation of materials, namely Thermally Activated Delayed Fluorescence (TADF) materials, has been developed, and these are able to use the small singlet–triplet energy gap to allow excitons on the triplet state to upconvert back to the single state, which improves the utilization of triplet excitons. These TADF materials can also reach 100% maximum internal quantum efficiency, but they have many problems, such as low color purity and serious efficiency roll-off. Therefore, researchers have designed hyperfluorescent materials, which possess high efficiency, high color purity, and a long lifetime, showing tremendous potential and application prospects in the field of display technology. This report takes hyperfluorescent OLEDs as the entry point and the molecular design and luminescence mechanism of hyperfluorescent materials are reviewed, considering blue, green, red, and white light. Full article

Thermally activated delayed fluorescence (TADF) often achieves high device efficiencies in organic light-emitting diodes. Here we develop TADF dyes, 1-H and 1-Me, based on an N,N-diphenylaminophenyl–phenylene–quinoxaline donor–π–acceptor system, which contains an unsubstituted 1,4-phenylene and a 2,5-dimethyl-1,4-phenylene π-spacer, respectively. In UV–vis absorption spectra in toluene at room temperature, 1-H showed a relatively intense shoulder band at 400 nm, whereas 1-Me had a weak, blue-shifted shoulder at 386 nm, indicating 1-Me adopts a more twisted π-conjugation system. On the other hand, the photoluminescence (PL) wavelength of 1-Me (λ_PL; 558 nm) under the same conditions was slightly red-shifted in comparison with that of 1-H (λ_PL; 552 nm), due to larger structural relaxation of 1-Me. From PL lifetime measurements, both the dyes showed TADF in 10 wt%-doped poly(methyl methacrylate) film, and their PL quantum yields were moderate (Φ_PL; ca. 0.5 at 300 K). As for the photokinetics, 1-Me exhibited larger rate constants for intersystem crossing and reverse intersystem crossing than 1-H due to the small excited-state singlet–triplet energy gap (ΔE_ST) of 1-Me. Furthermore, theoretical calculations indicated the triplet state of 1-Me is destabilized by localization of the spin density, resulting in the reduced ΔE_ST to facilitate TADF. Full article

Photosensitizers with high singlet oxygen (¹O₂) generation capacity under near-infrared (NIR) irradiation are essential and challenging for photodynamic therapy (PDT). A simple yet effective molecular design strategy is realized to construct 1 + 1 > 2 photosensitizers with synergistic effects by covalently integrating iridium complexes with cyanine via ether linkages, as well as introducing aldehyde groups to suppress non-radiative decay, named CHO−Ir−Cy. It is demonstrated that CHO−Ir−Cy successfully maintains the NIR absorption and emission originated from cyanine units and high ¹O₂ generation efficiency from the iridium complex part, which gives full play to their respective advantages while compensating for shortcomings. Density functional theory (DFT) calculations reveal that CHO−Ir−Cy exhibits a stronger spin–orbit coupling constant (ξ (S1, T1) = 9.176 cm⁻¹) and a reduced energy gap (ΔE = −1.97 eV) between triplet excited states (T₁) and first singlet excited states (S₁) compared to parent Ir−Cy or Cy alone, directly correlating with its enhanced ¹O₂ production. Remarkably, CHO−Ir−Cy demonstrates superior cellular internalization in 4T1 murine breast cancer cells, generating substantially elevated ¹O₂ yields compared to individual Ir−Cy/Cy under 808 nm laser irradiation. Such enhanced reactive oxygen species production translates into effective cancer cell ablation while maintaining favorable biocompatibility, significant phototoxicity and negligible dark toxicity. This molecular engineering strategy overcomes the inherent NIR absorption limitation of traditional iridium complexes and ensures their own high ¹O₂ generation ability through dye–metal synergy, establishing a paradigm for designing metal–organic photosensitizers with tailored photophysical properties for precision oncology. Full article

This study employs time-dependent density functional theory to explore the photophysical properties of a chiral iridium(III) complex designed as a photosensitizer for photodynamic therapy. Key properties analyzed include one-photon absorption energies, singlet–triplet energy gaps, spin–orbit coupling constants, and intersystem crossing rate constants. The potential for operation in a Type I PDT mechanism was assessed through ionization potential and electron affinity calculations. The results demonstrate that the complex is a promising PDT candidate, primarily operating in a Type II mechanism, while offering conditional viability for Type I photoreactivity under specific electronic and environmental conditions. Full article

Recent advances in electrochemiluminescence (ECL) leveraging thermally activated delayed fluorescence (TADF) have highlighted its potential for near-unity exciton harvesting. However, there are still very limited examples of TADF-ECL emitters. We present a rigid diboron-embedded multiple-resonance TADF emitter, which exhibits blue–green emission at 493 nm with a remarkably narrow bandwidth (FWHM = 22 nm) and minimized singlet-triplet energy gap (ΔE_ST = 0.2 eV), achieving a 67% photoluminescence quantum yield. DFT calculations confirm the short-range charge transfer, enabling narrowband emission. Co-reactant-dependent ECL shows that tripropylamine (TPrA) improves the ECL efficiency from 11% (annihilation) to 51%, while benzoyl peroxide (BPO) yields 1% due to poor radical stabilization. ECL spectra align with photoluminescence, confirming the singlet-state dominance without exciplex interference. TPrA enhances stable radical formation and energy transfer, whereas BPO induces non-radiative losses. These findings establish molecular rigidity and co-reactant selection as pivotal factors in developing high-performance TADF-ECL systems, providing fundamental guidelines for designing organic electrochemiluminescent materials with optimized exciton harvesting efficiency. Full article

Fluorenone derivatives represent promising candidates for electron-transport materials in organic electronic devices. Given that anionic species serve as electron-transfer carriers in electron-transport materials, it is highly desirable to isolate and characterize the radical anions and dianions of indenofluorened derivatives (IFO). In this work, the reduction of three indenofluorenedione derivatives (IFO, 1, 2 and 3) with potassium resulted in three radical anion salts (1K[(crypt-222)], 2K[(crypt-222)] and 3K) and one dianion salt (2[K(crypt-222)]₂). Single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy reveal that 1K[(crypt-222)] and 2K[(crypt-222)] have a full delocalization of the unpaired electron which is supported by calculated spin density distributions. We demonstrate that the polarization of electron spin in 3K is induced by potassium ion coordination through single-crystal X-ray structure analysis and DFT calculations, suggesting the electrostatic effect by potassium ion has a significant influence on the spin density modulation. Superconducting quantum interference device (SQUID) measurements and DFT calculations show that 2[K(crypt-222)]₂ has an open-shell singlet base with a large singlet-triplet energy gap (ΔE_os-t = −7.40 kcal mol⁻¹) so that the excited triplet state is not accessible at room temperature. Full article

Thermally activated delayed fluorescence (TADF) materials with high photoluminescence quantum yields and a fast reverse intersystem crossing (RISC) are of the highest interest for organic light-emitting diodes (OLEDs). In the past decade, triaryl boranes with multiple resonance effect (MR) have captured significant attention. The efficiency of MR-TADF emitters strongly depends on small singlet–triplet energy gaps (ΔE_ST), but also on large reverse intersystem crossing (RISC) rate constants (k_RISC). The latter effect has strongly been focused on very recently and has drawn attention to heavier elements, including sulfur and selenium, the large spin–orbit coupling (SOC) of which accelerates RISC effects. Within the context of MR-TADF emitters, the 5,9-X₂-13b-boranaphtho [3,2,1-de]anthracene scaffold (X-B-X, X = donor heteroatom, e.g., N, O, S, Se) has been recognized as a promising narrowband-emissive TADF material. However, the incorporation of sulfur and selenium as highly SOC-inducing elements has proven to be difficult. Most synthetic strategies apply protocols initially suggested by Hatakeyama to obtain nitrogen- and oxygen-doped materials. We present an alternative route over the established methodology, which affords highly sought-after sulfur- and selenium-doped materials with a high yield and purity. Full article

Cyclo[n]carbon (C_n) is one member of the all-carbon allotrope family with potential applications in next-generation electronic devices. By employing first-principles quantum transport calculations, we have investigated the electronic transport properties of single-molecule junctions of C_n, with n = 14, 16, 18, and 20, connected to two bulk gold electrodes, uncovering notable distinctions arising from the varying aromaticities. For the doubly aromatic C₁₄ and C₁₈ molecules, slightly deformed complexes at the singlet state arise after bonding with one Au atom at each side; in contrast, the reduced energy gaps between the highest occupied and the lowest unoccupied molecular orbitals due to the orbital reordering observed in the doubly anti-aromatic C₁₆ and C₂₀ molecules lead to heavily deformed asymmetric complexes at the triplet state. Consequently, spin-unpolarized transmission functions are obtained for the Au-C_14/18-Au junctions, while spin-polarized transmission appears in the Au-C_16/20-Au junctions. Furthermore, the asymmetric in-plane π-type hybrid molecular orbitals of the Au-C_16/20-Au junctions contribute to two broad but low transmission peaks far away from the Fermi level (E_f), while the out-of-plane π-type hybrid molecular orbitals dominate two sharp transmission peaks that are adjacent to E_f, thus resulting in much lower transmission coefficients at E_f compared to those of the Au-C_14/18-Au junctions. Our findings are helpful for the design and application of future cyclo[n]carbon-based molecular electronic devices. Full article

The oxidation of tetraselenatetracene (TSeT) by tetracyanoquinodimethane in the presence of dysprosium(III) tris(hexafluoroacetylacetonate), Dy^III(hfac)₃, produces black crystals of {TSeT_1.5}^●+[Dy^III(hfac)₄]⁻ (1) salt, which combines conducting and magnetic sublattices. It contains one-dimensional stacks composed of partially oxidized TSeT molecules (formal averaged charge is +2/3). Dimers and monomers can be outlined within these stacks with charge and spin density redistribution. The spin triplet state of the dimers is populated above 128 K with an estimated singlet-triplet energy gap of 542 K, whereas spins localized on the monomers show paramagnetic behavior. A semiconducting behavior is observed for 1 with the activation energy of 91 meV (measured by the four-probe technique for an oriented single crystal). The Dy^III ions coordinate four hfac⁻ anions in [Dy^III(hfac)₄]⁻, providing D_2d symmetry. Slow magnetic relaxation is observed for Dy^III under an applied static magnetic field of 1000 Oe, and 1 is a single-ion magnet (SIM) with spin reversal barrier U_eff = 40.2 K and magnetic hysteresis at 2 K. Contributions from Dy^III and TSeT^●+ paramagnetic species are seen in EPR. The Dy^III ion rarely manifests EPR signals, but such signal is observed in 1. It appears due to narrowing below 30 K and has g₄ = 6.1871 and g₅ = 2.1778 at 5.4 K. Full article

We report the absorption and photoluminescence spectra of GaSe single crystals in the near-edge region. The temperatures explored the range from 17 to 300 K. Specifically, at a temperature of 17 K, the photoluminescence spectrum reveals an interesting phenomenon: the Wannier-Mott exciton separates into two states. These states are a triplet state with an energy of 2.103 eV and a singlet state with an energy of 2.109 eV. The energy difference between these two states is 6 meV. Furthermore, the bound exciton (BX) can be localized at an energy of 2.093 eV. It is worth noting that its phonon replicas (BX-nLO) can be clearly distinguished up to the fourth order. Interestingly, the energy gaps between these replicas exhibit a consistent spacing of 7 ± 0.5 meV. This intriguing finding suggests a high-quality crystalline structure as well as a strong coupling between the phonon and BX-nLO. Additionally, at low temperatures, both the ground state (n = 1) at 2.11 eV and the excited state (n = 2) at 2.127 eV of free excitons can be observed. Full article

In this computational study, we investigate the electronic properties of zigzag graphene nano-parallelograms (GNPs), which are parallelogram-shaped graphene nanoribbons of various widths and lengths, using thermally assisted occupation density functional theory (TAO-DFT). Our calculations revealed a monotonic decrease in the singlet–triplet energy gap as the GNP length increased. The GNPs possessed singlet ground states for all the cases examined. With the increase of GNP length, the vertical ionization potential and fundamental gap decreased monotonically, while the vertical electron affinity increased monotonically. Some of the GNPs studied were found to possess fundamental gaps in the range of 1–3 eV, lying in the ideal region relevant to solar energy applications. Besides, as the GNP length increased, the symmetrized von Neumann entropy increased monotonically, denoting an increase in the degree of the multi-reference character associated with the ground state GNPs. The occupation numbers and real-space representation of active orbitals indicated that there was a transition from the nonradical nature of the shorter GNPs to the increasing polyradical nature of the longer GNPs. In addition, the edge/corner localization of the active orbitals was found for the wider and longer GNPs. Full article

We report on organoboron complexes characterized by very small energy gaps (ΔE_ST) between their singlet and triplet states, which allow for highly efficient harvesting of triplet excitons into singlet states for working as thermally activated delayed fluorescence (TADF) devices. Energy gaps ranging between 0.01 and 0.06 eV with dihedral angles of ca. 90° were registered. The spin–orbit couplings between the lowest excited S₁ and T₁ states yielded reversed intersystem crossing rate constants (K_RISC) of an average of 10⁵ s⁻¹. This setup accomplished radiative decay rates of ca. 10⁶ s⁻¹, indicating highly potent electroluminescent devices, and hence, being suitable for application as organic light-emitting diodes. Full article

The effect on the photophysical properties of sulfur- and selenium-for-oxygen replacement in the skeleton of the oxo-4-dimethylaminonaphthalimide molecule (DMNP) has been explored at the density functional (DFT) level of theory. Structural parameters, excitation energies, singlet–triplet energy gaps (ΔE_S-T), and spin–orbit coupling constants (SOC) have been computed. The determined SOCs indicate an enhanced probability of intersystem crossing (ISC) in both the thio- and seleno-derivatives (SDMNP and SeDMNP, respectively) and, consequently, an enhancement of the singlet oxygen quantum yields. Inspection of Type I reactions reveals that the electron transfer mechanisms leading to the generation of superoxide is feasible for all the compounds, suggesting a dual Type I/Type II activity. Full article

In this study, we developed two thermally activated delayed fluorescence (TADF) emitters, ICzCN and ICzCYP, to apply to organic light-emitting diodes (OLEDs). These emitters involve indolocarbazole (ICz) donor units and nicotinonitrile acceptor units with a twisted donor-acceptor-donor (D-A-D) structure for small singlet (S₁) and triplet (T₁) state energy gap (ΔE_ST) to enable efficient exciton transfer from the T₁ to the S₁ state. Depending on the position of the cyano-substituent, ICzCN has a symmetric structure by introducing donor units at the 3,5-position of isonicotinonitrile, and ICzCYP has an asymmetric structure by introducing donor units at the 2,6-position of nicotinonitrile. These emitters have different properties, such as the maximum luminance (L_max) value. The L_max of ICzCN reached over 10000 cd m⁻². The external quantum efficiency (η_ext) was 14.8% for ICzCN and 14.9% for ICzCYP, and both achieved a low turn-on voltage (V_on) of less than 3.4 eV. Full article