Structural Optimization of BODIPY Derivatives: Achieving Stable and Long-Lived Green Emission in Hyperfluorescent OLEDs.

Boron dipyrromethene (BODIPY) derivatives are widely studied as terminal emitters in organic light-emitting diodes (OLED) due to their narrow emission and high photoluminescence quantum yield (PLQY). However, the strategy for precisely tuning their emission toward a high color purity is still challenging. Herein, we developed a new design strategy to regulate the emission of BODIPY derivatives by modifying the electronic and steric dominance using functionalities, such as nitrile, pentafluorophenyl, diethyl, and monobenzyl. These rational modifications yielded a series of four novel green BODIPY emitters, namely, tPN-BODIPY, tPPP-BODIPY, tPBn-BODIPY, and tPEN-BODIPY, each benefited with a tuned emissions range of 517 to 542 nm with a narrow fwhm of 25 nm and high photoluminescence quantum yield up to 96%. Among these synthesized BODIPYs, an unsymmetrical tPBn-BODIPY was chosen as a final dopant (FD) to explore its application in OLED devices. The fabricated TADF sensitized fluorescence-OLED (TSF-OLED) exhibits a narrow band pure green emission at 531 nm with corresponding CIE coordinates of (x, y) = (0.27, 0.68) and a maximum external quantum efficiency (EQE) of 20%. Furthermore, the TSF-OLED displayed an exceptionally prolonged device operational lifetime (LT90) of 210 h at an initial luminescence of 3000 cd m-2.

Forthcoming hyperfluorescence display technology: relevant factors to achieve high-performance stable organic light emitting diodes.

Over the decade, there have been developments in purely organic thermally activated delayed fluorescent (TADF) materials for organic light-emitting diodes (OLEDs). However, achieving narrow full width at half maximum (FWHM) and high external quantum efficiency (EQE) is crucial for real display industries. To overcome these hurdles, hyperfluorescence (HF) technology was proposed for next-generation OLEDs. In this technology, the TADF material was considered a sensitizing host, the so-called TADF sensitized host (TSH), for use of triplet excitons via the reverse intersystem crossing (RISC) pathway. Since most of the TADF materials show bipolar characteristics, electrically generated singlet and triplet exciton energies can be transported to the final fluorescent emitter (FE) through Förster resonance energy transfer (FRET) rather than Dexter energy transfer (DET). This mechanism is possible from the S1 state of the TSH to the S1 state of the final fluorescent dopant (FD) as a long-range energy transfer. Considering this, some reports are available based on hyperfluorescence OLEDs, but the detailed analysis for highly efficient and stable devices for commercialization was unclear. So herein, we reviewed the relevant factors based on recent advancements to build a highly efficient and stable hyperfluorescence system. The factors include an energy transfer mechanism based on spectral overlapping, TSH requirements, electroluminescence study based on exciplex and polarity system, shielding effect, DET suppression, and FD orientation. Furthermore, the outlook and future positives with new directions were discussed to build high-performance OLEDs.

Excited State and Non-linear Optical Properties of NIR Absorbing ß-Thiophene-Fused BF2-Azadipyrromethene Dyes-Computational Investigation.

Density functional theory and time-dependent density functional theory computations were used to understand the electronic and photophysical parameters of NIR ß-thiophene-fused BF2-azadipyrromethene dyes. The computed data are in good agreement with those obtained experimentally and they provide insights into the origin of red shifted optical spectra compared to the parent aza-BODIPY, low Stokes shift, non-linear optical responses and quantitative description of the singlet-triplet energy gap. The resultant decrease in the HOMO - LUMO energy gap is responsible for the red shift. The possible use as non-linear optical materials is supported by large enhancement in the non-linear optical properties. On the basis of vertical triplet energies, their possible potential therapeutic use as a photosensitizer in photodynamic therapy is proposed. The singlet-triplet energetic gaps suggest that the ß-thiophene-fused BF2-azadipyrromethene dyes can act as a sensitizer to produce an efficient generation of singlet oxygen. Their optimal use as an efficient singlet fission materials has been proposed on the basis of excitation energies in the ground, lowest singlet and triplet excited states.

Investigating the excited state optical properties and origin of large stokes shift in Benz[c,d]indole N-Heteroarene BF2 dyes with ab initio tools.

Density Functional Theory and Time Dependent Density Functional Theory computations reveal experimental trends accurately and provide an insight into the origin of red shifted optical spectra, large Stokes shift, nonlinear optical responses and quantitative description of the singlet-triplet energy gap of recently synthesized highly fluorescent membrane permeable benz[c,d]indole N-heteroarene BF2 rigidified BBN and BBC dyes. Our results benchmark the importance of the DFT functionals and polarization functions using the accurate basis set for the calculations of excitation energies, band gaps, dipole moment, non-linear optical properties and geometrical parameters. The anomalous increase in dipole moment in the excited state and pronounced geometric distortion are found to be responsible for the increased Stokes shift in BBN dyes. The resultant decrease in the HOMO-LUMO energy gap was found to be responsible for the red shift in BBC dyes. Enhanced nonlinear optical properties and inverse relationship between the Stokes shift and static hyperpolarizability were found in these dyes. Their possible potential therapeutic use as a photosensitizer in photodynamic therapy is proposed on the basis of vertical triplet energies resulting in the range of 0.78 to 0.88eV. The singlet-triplet energetic gaps suggest that the simple variation of the N-heteroarenes or their post functionalization can lead to the efficient generation of singlet oxygen. Further, we compared these new class of dyes with conventional aza-BODIPY and BODIPY dyes, thereby confirming their use as alternative promising candidates for nonlinear optics, triplet sensitizers, and imaging.

Carbazole-Linked Near-Infrared Aza-BODIPY Dyes as Triplet Sensitizers and Photoacoustic Contrast Agents for Deep-Tissue Imaging.

Four new N-ethylcarbazole-linked aza-boron-dipyrromethene (aza-BODIPY) dyes (8 a,b and 9 a,b) were synthesized and characterized. The presence of the N-ethylcarbazole moiety shifts their absorption and fluorescence spectra to the near-infrared region, λ≈650-730 nm, of the electromagnetic spectrum. These dyes possess strong molar absorptivity in the range of 3-4×104 m-1 cm-1 with low fluorescence quantum yields. The triplet excited state and singlet oxygen generation of these dyes were enhanced upon iodination at the core position. The core-iodinated dyes 9 a,b showed excellent triplet quantum yields of about 90 and 75 %, with singlet oxygen generation efficiency of about 70 and 60 % relative to that of the parent dyes. Derivatives 8 a,b showed dual absorption profiles, in contrast to dyes 9 a,b, which had the characteristic absorption band of aza-BODIPY dyes. DFT calculations revealed that the electron density was spread over the iodine and dipyrromethene plane of 9 a,b, whereas in 8 a,b the electron density was distributed on the carbazole group and dipyrromethene plane of aza-BODIPY. The uniqueness of these aza-BODIPY systems is that they exhibit efficient triplet-state quantum yields, high singlet oxygen generation yields, and good photostability. Furthermore, the photoacoustic (PA) characteristics of these aza-BODIPY dyes was explored, and efficient PA signals for 8 a were observed relative to blood serum with in vitro deep-tissue imaging, thereby confirming its use as a promising PA contrast agent.

Fluorescent styryl dyes based on novel 4-methoxy-9-methyi-9H-carbazole-3-carbaldehyde--synthesis, photophysical properties and DFT computations.

Novel carbazole based styryl derivatives (6a-6c) having styryl group at third position and a methoxy substitution were synthesized by condensing 4-methoxy-9-methyl-9H-carbazole-3-carbaldehyde 3 and different active methylene derivatives (5a-5c). Evaluated photophysical properties of these synthesized novel chromophores, studied the effect of solvent polarity on absorption, emission and quantum yield of these styryl derivatives. DFT and TD-DFT computations are carried out to study structural, molecular, electronic and photophysical parameters of dyes. The ratio of ground state to excited state dipole moment was calculated using Bakhshiev and Kawski-Chamma-Viallet correlations.