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1.
Four compounds (TM-1~4) based on N-(4-trifluoromethylphenyl)phenothiazine-S,S-dioxide and N-[3,5-bis(trifluoromethyl)phenyl]phenothiazine-S,S-dioxide are synthesized by Buchwald-Hartwig cross coupling reaction. The effect of different substituents in acceptors on the electronic, photophysical and electrochemical properties are studied by UV–Vis, fluorescence spectroscopy, cyclic voltammetry curves and theoretical calculations. The energy gaps (ΔEST) between singlet excited states (S1) and triplet excited states (T1) of these compounds decrease by addition of one para-substituted CF3 or two meta-substituted CF3 on N-phenyl in order to enhance the electron-withdrawing capability of the acceptors. Small ΔEST of these compounds range from 0.09 eV to 0.18 eV. TM-2~4 exhibit thermally activated delayed fluorescence (TADF) characteristics with short delayed fluorescence lifetimes (τd) within 0.69-1.16 μs. TM-3 emits blue light with an emission wavelength of 475 nm.  相似文献   

2.
Rational manipulation of energy utilization from excited-state radiation of theranostic agents with a donor–acceptor structure is relatively unexplored. Herein, we present an effective strategy to tune the exciton dynamics of radiative excited state decay for augmenting two-photon nanotheranostics. As a proof of concept, two thermally activated delayed fluorescence (TADF) molecules with different electron-donating segments are engineered, which possess donor–acceptor structures and strong emissions in the deep-red region with aggregation-induced emission characteristics. Molecular simulations demonstrate that change of the electron-donating sections could effectively regulate the singlet–triplet energy gap and oscillator strength, which promises efficient energy flow. A two-photon laser with great permeability is used to excite TADF NPs to perform as theranostic agents with singlet oxygen generation and fluorescence imaging. These unique performances enable the proposed TADF emitters to exhibit tailored balances between two-photon singlet oxygen generation and fluorescence emission. This result demonstrates that TADF emitters can be rationally designed as superior candidates for nanotheranostic agents by the custom controlling exciton dynamics.

Exciton dynamics can be manipulated rationally in the design of TADF materials for nanotheranostics. Regulating the ΔEST and f promises efficient energy flow for tailoring balances between singlet oxygen generation and fluorescence emission.  相似文献   

3.
A series of novel hyperbranched polymers(HBPs) consisting of a 2,7-subsituted 9-(heptadecan-9-yl)-9H-carbazole unit(A_2+A_2') and a tetra-substituted green thermally activated delayed fluorescence(TADF) dye of 2,3,5,6-tetra(9Hcarbazol-9-yl)-4-pyridinecarbonitrile(4CzCNPy, B4) have been synthesized via Suzuki cross-coupling reaction following an "A2+A2'+B_4" method. The polymers are named according to the polymerization ratio of 4CzCNPy monomer(5 mol%, 10 mol% and 15 mol% for HBPs of P2-P4 respectively, and 0 mol% for the control linear polymer P1). Their thermal, optoelectronic and electrochemical properties have been characterized by a combination of techniques. All the polymers exhibit high thermal stability with the decomposition temperatures(Td) above 400 ℃ and glass transition temperatures(Tg) up to 98 ℃. Unfortunately, the incorporation of TADF moiety into these HBP materials induced non-TADF characteristics. However, when the HBPs functionalized as the host for our previously developed 4CzCNPy TADF dopant in solution processed devices, maximum external quantum efficiency of 5.7% and current efficiency of 17.9 cd/A have been achieved in P3-based device, which is significantly higher than those of 1.5% and 4.2 cd/A for the linear polymer P1.  相似文献   

4.
An organic light emitting diode based on thermally activated delayed fluorescence (TADF) has been produced using a spirobifluorene derivative (Spiro-CN) having the donor-acceptor moieties as an emitter.  相似文献   

5.
Efficient thermally activated delayed fluorescence (TADF) has been characterized for a carbazole/sulfone derivative in both solutions and doped films. A pure blue organic light emitting diode (OLED) based on this compound demonstrates a very high external quantum efficiency (EQE) of nearly 10% at low current density. Because TADF only occurs in a bipolar system where donor and acceptor centered (3)ππ* states are close to or higher than the triplet intramolecular charge transfer ((3)CT) state, control of the π-conjugation length of both donor and acceptor is considered to be as important as breaking the π-conjugation between them in blue TADF material design.  相似文献   

6.
Exploration of novel organic luminophores that exhibit thermally activated delayed fluorescence (TADF) in the aggregated state is very crucial for advance of delayed luminescence-based applications such as time-gated bio-sensing and temperature sensing. We report herein that synthesis, photophysical properties, molecular and crystal structures, and theoretical calculations of 2,6-bis (diarylamino)benzophenones. Absorption spectra in solution and calculations using density functional theory (DFT) method revealed that the optical excitation took place through intramolecular charge-transfer from one diarylamino moiety to an aroyl group. While the benzophenones did not luminesce in solution, the solids of the benzophenones emitted green light with moderate-to-good quantum yields. Thus, the benzophenones exhibit aggregation-induced emission. Based on the lifetime measurement, the green emission of the solids was found to include TADF. The emergence of the TADF is supported by the small energy gap between the excited singlet and triplet states, which was estimated by time-dependent DFT calculations. Thin films of poly(methyl methacrylate) doped by the benzophenones also showed green prompt and delayed fluorescence whose lifetimes were in the order of microseconds. Linear correlation between logarithm value of TADF lifetime and temperature was observed with the benzophenone in powder, suggesting that the benzophenones can serve as molecular thermometers workable under aqueous conditions.  相似文献   

7.
Zhang  Yunge  Zhang  Dongdong  Tsuboi  Taiju  Qiu  Yong  Duan  Lian 《中国科学:化学(英文版)》2019,62(3):393-402
Science China Chemistry - Albeit their high efficiencies, the operational stability of the organic light emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) emitters is...  相似文献   

8.
9.
A thermally activated delayed fluorescence (TADF) white organic light-emitting diode (WOLED) holds great promise for low-cost, large-scale lighting applications. Nevertheless, manipulating exciton allocation in a white TADF single layer is still a challenge. Herein, we demonstrate that the exciton kinetic process of dually doped white TADF films is strongly dependent on the grid regularity of the host matrix. Intermolecular hydrogen bonds (IHBs) are used to weave the matrices of two host molecules DPEQPO and DPSQPO featuring four phosphine oxide (PO) groups and different IHB orientations. The DPSQPO matrix forms regular grids to uniformly disperse and separate dopants, while DPEQPO exhibits chaotic IHBs, in turn inducing a heterogeneous dopant distribution. As a consequence, in both photoluminescence and electroluminescence processes, in contrast to DPEQPO hosted systems with comparable singlet Förster resonance energy transfer and triplet Dexter energy transfer, DPSQPO provides a FRET-predominant exciton allocation between blue and yellow dopants, which markedly suppresses triplet quenching and improves the white color purity, resulting in a state-of-the-art external quantum efficiency up to 24.2% of its single-emissive-layer pure-white TADF diode, in contrast to 16.0% for DPEQPO based analogs. These results indicate the significance of host engineering for exciton kinetics and suggest the feasibility of host grid design for developing high-performance TADF lighting.

A thermally activated delayed fluorescence (TADF) white organic light-emitting diode (WOLED) holds great promise for low-cost, large-scale lighting applications.  相似文献   

10.
Different from the conventional piezochromic materials with a mono-redshift of single emission, our well-designed molecule demonstrates a sensitive turn-on and color-tunable piezochromic luminescence in response to the hydrostatic pressure. The molecule PXZ-W-SOF possesses dual-emission and pressure-induced bidirectional shifting characteristics. On the basis of in-depth experimental studies, on one hand, it is confirmed that the origin of the dual-emission behavior is the intramolecular charge transfer, namely thermally activated delayed fluorescence (TADF), and the intermolecular excimer; on the other hand, the emission of the excimer exhibits three-step variations with increasing pressure, which is mainly attributed to the molecular structure and its crystal packing state. The remarkable color change of PXZ-W-SOF from sky-blue to green to deep-blue during the whole process of boosting and releasing pressure is a result of intramolecular and intermolecular energy-transfer interactions. The PXZ-W-SOF molecular model is an extremely rare example of highly sensitive fluorescence tuning driven by TADF and excimer conversion under mechanical stimulation, thus providing a novel mechanism for the field of piezochromism. The unique molecular design also offers a new idea for rare deep-blue and ultraviolet TADF materials.

A high-contrast luminescent material exhibits dual-emission and pressure-induced bidirectional shifting, originating from the cooperative effects of TADF and excimers. It provides a novel mechanism for the piezochromic behavior.  相似文献   

11.
《中国化学快报》2019,30(11):1955-1958
The highest efficiency thermally activated delayed fluorescence(TADF) emitters in OLEDs are mostly based on twisted donor/acceptor(D/A) type organic molecules.Herein,we report the rational molecular design on twisted all ortho-linked carbazole/oxadiazole(Cz/OXD) hybrids with tunable D-A interactions by adjusting the numbers of donor/acceptor units and electron-donating abilities.Singlet-triplet energy bandgaps(ΔE_(ST)) are facilely tuned from~0.4,0.15 to~0 eV in D-A,D-A-D to A-D-A type compounds.This variation correlates well with triplet-excited-state frontier orbital spatial separation efficiency.NonTADF feature with solid state photoluminescence quantum yield(PLQY)10% is observed in D-A type2 CzOXD and D-A-D type 4 CzOXD.Owing to the extremely low ΔE_(ST) for efficient reverse intersystem crossing,strong TADF with PLQY of 71%-92% is achieved in A-D-A type 4 CzDOXD and 4 tCzDOXD.High external quantum efficiency from 19.4% to 22.6% is achieved in A-D-A typed 4 CzDOXD and 4 tCzDOXD.  相似文献   

12.
正Organic light-emitting diodes(OLEDs)have attracted considerable attentions from both academia and industry for decades because of their potential applications in full color flat-panel displays and solid state lightings.Since2009[1],thermally activated delayed fluorescence(TADF)OLEDs have drawn intense attention due to the utilization of low-cost organic luminogens by harvesting all singlet and triplet excitons to theoretically reach 100%internal  相似文献   

13.
All ortho-linked D-A and D-A-D molecules exhibit non-TADF feature due to broad spatial overlap at triplet excited state for large △EST,while A-D-A compounds show strong TADF property owing to efficient spatial separation for small △EST.  相似文献   

14.
运用含时密度泛函理论(TD-DFT)方法,在以苯为溶剂的可极化连续模型(PCM)下,研究了2,4,6-三(9-咔唑基)-间苯二腈(3CzIPN)分子发生热活化延迟荧光(TADF)的反应机制.计算结果表明,3CzIPN分子的单-三态能量差非常小,仅为0.124 eV,这对反系间窜越(RISC)非常有利.此外,3CzIPN分子的RISC速率达到了104数量级,表明3CzIPN分子可能是一个潜在的TADF发射体.  相似文献   

15.
《中国化学快报》2023,34(2):107515
Triplet-triplet annihilation (TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared (NIR)-to-blue upconverted emission is preferred for most of the practical applications, but developing a NIR-to-blue TTA upconversion system is a challenging task in photochemistry. In this work, a thermally activated delayed fluorescence (TADF) material with intense visible-to-NIR absorption is demonstrated that shows a longer triplet state lifetime (32 µs) and high triplet state energy (ET = 1.55 eV). For the first time, a heavy atom-free NIR (λex > 650 nm) to blue (λem< 460 nm) TTA upconversion system was devised, employing the dimeric borondifluoride curcuminoid TADF material as triplet photosensitizer (PS) and a large anti-Stokes shift (0.88 eV) along with moderate upconversion yield was achieved. Our work provides the solution and guidance for the future development of purely organic heavy atom-free NIR activating TTA upconversion system for a wide array of applications.  相似文献   

16.
We report the first observation of thermally activated delayed fluorescence (TDF) from an excited-state intramolecular proton-transfer (ESIPT) molecule, a hydroxyl-substituted tetraphenyl imidazole derivative (HPI-Ac), in degassed solutions as well as in low-temperature organic matrixes. In the absence of oxygen, the blue emission of an identical spectral feature was observed in the nanosecond ( approximately 4.4 ns) and microsecond ( approximately 25 micros) time domains, and the fluorescence intensity increased with temperature. From the temperature dependence of the time-resolved spectra of HPI-Ac, the energy gap between the first-excited singlet state and the lowest triplet state was determined to be 7.6 +/- 0.3 kJ/mol (630 +/- 25 cm-1), and the limiting rate constant of intrinsic reverse intersystem crossing was estimated to be 1.3 (+/-0.5) x 107 s-1.  相似文献   

17.
In this paper, we propose a strategic molecular design of closo-o-carborane-based donor–acceptor dyad system that exhibits thermally activated delayed fluorescence (TADF) in the solution state at ambient temperature. Planar 9,9-dimethyl-9H-fluorene-based compounds with closo- and nido-o-carborane cages appended at the C2-, C3-, and C4-positions of each fluorene moiety (closo-type: 2FC, 3FC, 4FC, and 4FCH, and nido-type: nido-4FC = [nido-form of 4FC]·[NBu4]) were prepared and characterized. The solid-state molecular structure of 4FC exhibited a significantly distorted fluorene plane, which suggests the existence of severe intramolecular steric hindrance. In photoluminescence measurements, 4FC exhibits a noticeable intramolecular charge transition (ICT)-based emission in all states (solution at 298 K and 77 K, and solid states); however, emissions by other closo-compounds were observed in only the rigid state (solution at 77 K and film). Furthermore, nido-4FC did not exhibit emissive traces in any state. These observations verify that all radiative decay processes correspond to ICT transitions triggered by closo-o-carborane, which acts as an electron acceptor. Relative energy barriers calculated by TD-DFT as dihedral angles around o-carborane cages change in closo-compounds, which indicates that the structural formation of 4FC is nearly fixed around its S0-optimized structure. This differs from that for other closo-compounds, wherein the free rotation of their o-carborane cages occurs easily at ambient temperature. Such rigidity in the structural geometry of 4FC results in ICT-based emission in solution at 298 K and enhancement of quantum efficiency and radiative decay constants compared to those for other closo-compounds. Furthermore, 4FC displays short-lived (∼0.5 ns) and long-lived (∼30 ns) PL decay components in solution at 298 K and in the film state, respectively, which can be attributed to prompt fluorescence and TADF, respectively. The calculated energy difference (ΔEST) between the first excited singlet and triplet states of the closo-compounds demonstrate that the TADF characteristic of 4FC originates from a significantly small ΔEST maintained by the rigid structural fixation around its S0-optimized structure. Furthermore, the strategic molecular design of the o-carborane-appended π-conjugated (D–A) system, which forms a rigid geometry due to severe intramolecular steric hindrance, can enhance the radiative efficiency for ICT-based emission and trigger the TADF nature.

The first example of a closo-o-carboranyl compound demonstrating thermally activated delayed fluorescence (TADF) nature in solution is shown, and a strategic molecular design of a closo-o-carboranyl luminophore to exhibit TADF is proposed.  相似文献   

18.
Nondoped organic light-emitting diodes (OLEDs) have drawn immense attention due to their merits of process simplicity, reduced fabrication cost, etc. To realize high-performance nondoped OLEDs, all electrogenerated excitons should be fully utilized. The thermally activated delayed fluorescence (TADF) mechanism can theoretically realize 100% internal quantum efficiency (IQE) through an effective upconversion process from nonradiative triplet excitons to radiative singlet ones. Nevertheless, exciton quenching, especially related to triplet excitons, is generally very serious in TADF-based nondoped OLEDs, significantly hindering the pace of development. Enormous efforts have been devoted to alleviating the annoying exciton quenching process, and a number of TADF materials for highly efficient nondoped devices have been reported. In this review, we mainly discuss the mechanism, exciton leaking channels, and reported molecular design strategies of TADF emitters for nondoped devices. We further classify their molecular structures depending on the functional A groups and offer an outlook on their future prospects. It is anticipated that this review can entice researchers to recognize the importance of TADF-based nondoped OLEDs and provide a possible guide for their future development.

The mechanism, exciton leaking channels, and reported molecular design strategies of TADF emitters for high-performance nondoped OLEDs are summarized. Their molecular structures depending on the functional A groups are further classified.  相似文献   

19.
During the past decade, the discovery of thermally activated delayed fluorescence (TADF) materials has significantly boosted the development of organic light-emitting diode (OLED) technology. Compared with small-molecule and polymeric TADF materials, TADF dendrimers have emerged as promising emitters for solution-processed OLEDs because they have the integrated advantages of TADF small molecules and polymers in achieving high efficiency, excellent solution processability, and precise molecular structures. In recent years, TADF dendrimers have experienced important advances in molecular design, mechanism exploration and device performance. Herein, we present a comprehensive review of solution-processable TADF dendrimers, mainly focusing on their molecular design principles and structure–property correlations. The advanced device performances of these dendrimers are also summarized. Finally, we proposed the prospects and challenges on the development of TADF dendrimers.  相似文献   

20.
郭续更  冯松燕 《化学研究》2019,30(2):111-116
基于两个实验报道的热活化延迟荧光(TADF)分子(DPO-TXO2和DDMA-TXO2),通过改变供体基团,理论设计出一种新分子DPPA-TXO2.采用半经典的Marcus理论表达式,以及密度泛函理论和含时密度泛函理论,研究了改变这三个分子供体单元对其TADF机制的影响.研究结果表明,这三个分子的单三态能隙差都极小,仅为0.01或0.02 eV,这确保了从三重态到单重态的反系间窜跃过程的顺利进行.此外,理论预测的DPO-TXO2分子的反系间窜跃速率为5.67×10~5 s~(-1),跟实验测量值(1.04×10~6 s~(-1))非常吻合,并能够与其辐射失活速率(2.79×10~5 s~(-1))竞争.值得注意的是,新设计的DPPA-TXO2分子的反系间窜跃速率也达到了10~3数量级,是一个潜在的TADF发光体.  相似文献   

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