Organic light-emitting diodes (OLEDs) have their performance limited by the number of emissive singlet states created upon charge recombination (25%). Recently, a novel strategy has been proposed, based on thermally activated up-conversion of triplet to singlet states, yielding delayed fluorescence (TADF), which greatly enhances electroluminescence. The energy barrier for this reverse intersystem crossing mechanism is proportional to the exchange energy (ΔEST ) between the singlet and triplet states; therefore, materials with intramolecular charge transfer (ICT) states, where it is known that the exchange energy is small, are perfect candidates. However, here it is shown that triplet states can be harvested with 100% efficiency via TADF, even in materials with ΔEST of more than 20 kT (where k is the Boltzmann constant and T is the temperature) at room temperature. The key role played by lone pair electrons in achieving this high efficiency in a series of ICT molecules is elucidated. The results show the complex photophysics of efficient TADF materials and give clear guidelines for designing new emitters.
Thiacalixarenes, a subclass of "third generation" calixarenes, exhibit many interesting features such as enlarged ring size, facile chemical modification, and metal complexation due to the presence of bridging sulfur atoms. The thiacalixarene scaffold is a unique host with vast possibilities for functionalization not only at the upper and lower rim but also at the bridging sulfide groups. Modified thiacalixarenes have been used for many applications such as the detection and separation of biologically important cations, anions, and bio-analytes, mimicking molecular logic gates and devices, and synthesis of self-assembled coordination cages, multinuclear complexes, magnetic materials and luminescent materials. This review article summarizes recent developments in the derivatization methods of thiacalixarenes and their utilization in various applications.
Pentacenequinone derivative 3 forms luminescent supramolecular aggregates both in bulk as well as in solution phase. In bulk phase at high temperature, long-range stacking of columns leads to formation of stable and ordered columnar mesophase. Further, derivative 3 works as sensitive chemosensor for picric acid (PA) and gel-coated paper strips detect PA at nanomolar level and provide a simple, portable, and low-cost method for detection of PA in aqueous solution, vapor phase, and in contact mode.
We
expose significant changes in the emission color of carbazole-based
thermally activated delayed fluorescence (TADF) emitters that arise
from the presence of persistent dimer states in thin films and organic
light-emitting diodes (OLEDs). Direct photoexcitation of this dimer
state in 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) reveals the significant influence of dimer species
on the color purity of its photoluminescence and electroluminescence.
The dimer species is sensitive to the sample preparation method, and
its enduring presence contributes to the widely reported concentration-mediated
red shift in the photoluminescence and electroluminescence of evaporated
thin films. This discovery has implications on the usability of these,
and similar, molecules for OLEDs and explains disparate electroluminescence
spectra presented in the literature for these compounds. The dimerization-controlled
changes observed in the TADF process and photoluminescence efficiency
mean that careful consideration of dimer states is imperative in the
design of future TADF emitters and the interpretation of previously
reported studies of carbazole-based TADF materials.
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