Intramolecular charge transfer (ICT) occurs when photoexcitation causes electron transfer from an electron donor to an electron acceptor within the same molecule and is usually stabilized by decoupling of the donor and acceptor through an orthogonal twist between them. Thermally activated delayed fluorescence (TADF) exploits such twisted ICT states to harvest triplet excitons in OLEDs. However, the highly twisted conformation of TADF molecules results in limited device lifetimes.
View Article and Find Full Text PDFThe efficiency of thermally activated delayed fluorescence (TADF) in organic materials relies on rapid intersystem crossing rates and fast conversion of triplet (T) excitons into a singlet (S) state. Heavy atoms such as sulfur or selenium are now frequently incorporated into TADF molecular structures to enhance these properties by increased spin-orbit coupling [spin orbit coupling (SOC)] between the T and S states. Here a series of donor-acceptor (D-A) molecules based on 12-benzo[4,5]thieno[2,3-]carbazole and dicyanopyridine is compared with their nonsulfur control molecules designed to probe such SOC effects.
View Article and Find Full Text PDFOptical pump-probe techniques allow for an in-depth study of dark excited states. Here, we utilize them to map and gain insights into the excited states involved in the thermally activated delayed fluorescence (TADF) mechanism of a benchmark TADF emitter . The results identify different electronic excited states involved in the key TADF transitions and their nature by combining pump-probe and photoluminescence measurements.
View Article and Find Full Text PDFACS Appl Mater Interfaces
May 2023
Extensive research has been devoted to the development of thermally activated delayed fluorescence emitters, especially those showing pure-blue emission for use in lighting and full-color display applications. Toward that goal, herein we report a novel weak donor, 1,4-azaborine (AZB), with complementary electronic and structural properties compared to the widely used dimethylacridan (DMAC) or carbazole (Cz) donors. Coupled with a triazine acceptor, is the direct structural analogue of the high-performance and well-studied green TADF emitter and has Δ = 0.
View Article and Find Full Text PDFMetal-free organic emitters that display solution-phase room temperature phosphorescence (sRTP) remain exceedingly rare. Here, we investigate the structural and photophysical properties that support sRTP by comparing a recently reported sRTP compound (BTaz-Th-PXZ) to two novel analogous materials, replacing the donor group by either acridine or phenothiazine. The emissive triplet excited state remains fixed in all three cases, while the emissive charge-transfer singlet states (and the calculated paired charge-transfer T state) vary with the donor unit.
View Article and Find Full Text PDFMost organic room-temperature phosphorescence (RTP) emitters do not show their RTP in solution. Here, we incorporated sulfur-containing thiophene bridges between the donor and acceptor moieties in D A-type tristriazolotriazines (TTTs). The thiophene inclusion increased the spin-orbit coupling associated with the radiative T →S pathway, allowing RTP to be observed in solution for all compounds, likely assisted by protection of the emissive TTT-thiophene core from the environment by the bulky peripheral donors.
View Article and Find Full Text PDFTriplet harvesting under ambient conditions plays a crucial role in improving the luminescence efficiency of purely organic molecular systems. This requires elegant molecular designs that can harvest triplets either via room temperature phosphorescence (RTP) or by thermally activated delayed fluorescence (TADF). In this context, here we report a donor core-substituted pyromellitic diimide (acceptor) derivative as an efficient charge-transfer molecular design from the arylene diimide family as a triplet emitter.
View Article and Find Full Text PDFArylene diimide derived ambient organic phosphors are seldom reported despite their potential structural characteristics to facilitate the triplet harvesting. In this context, highly efficient room temperature phosphorescence (RTP) from simple, heavy-atom substituted pyromellitic diimide derivatives in amorphous matrix and crystalline state is reported here. Multiple intermolecular halogen bonding interactions among these phosphors, such as halogen-carbonyl and halogen-π resulted in the modulation of phosphorescence, cyan emission from monomeric state and orange-red emission from its aggregated state, to yield twin RTP emission.
View Article and Find Full Text PDFAmbient afterglow luminescence from metal-free organic chromophores would provide a promising alternative to the well-explored inorganic phosphors. However, the realization of air-stable and solution-processable organic afterglow systems with long-lived triplet or singlet states remains a formidable challenge. In the present study, a delayed sensitization of the singlet state of organic dyes via phosphorescence energy transfer from organic phosphors is proposed as an alternative strategy to realize "afterglow fluorescence".
View Article and Find Full Text PDFUnprecedented ambient triplet-mediated emission in core-substituted naphthalene diimide (cNDI) derivatives is unveiled via delayed fluorescence and room temperature phosphorescence. Carbazole core-substituted cNDIs, with a donor-acceptor design, showed deep-red triplet emission in solution processable films with high quantum yield. This study, with detailed theoretical calculations and time-resolved emission experiments, enables new design insights into the triplet harvesting of cNDIs; an important family of molecules which has been, otherwise, extensively been investigated for its n-type electronic character and tunable singlet fluorescence.
View Article and Find Full Text PDFAmbient solution and amorphous state room temperature phosphorescence (RTP) from purely organic chromophores is rarely achieved. Remarkable stabilization of triplet excitons is realized to obtain deep red phosphorescence in water and in amorphous film state under ambient conditions by a unique supramolecular hybrid assembly between inorganic laponite clay and heavy atom core substituted naphthalene diimide (NDI) phosphor. Structural rigidity and oxygen tolerance of the inorganic template along with controlled molecular organization via supramolecular scaffolding are envisaged to alleviate the unprecedented aqueous phase phosphorescence.
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