Synthesis of π-Extended [1.1]Paracyclophanes, [1.1][n]PCP (n = 2, 3, and 4), and Their Through-space Conjugation.

[1.1][n]Paracyclophanes ([1.1][n]PCPs) (3) with n = 2, 3, and 4, which consist of two [n]paraphenylene units connected by methylene bridges, were synthesized using short synthetic pathways with good overall yields. Single-crystal X-ray diffraction analyses reveal that the paraphenylene unit in 3 is bent, resulting in an elliptic core structure of 3. The facing bridgehead carbons of the paraphenylene units are separated by a distance much shorter than the sum of the van der Waals radii of sp2-carbon atoms. UV-vis absorption spectra, fluorescence spectra, electrochemical measurements, and theoretical calculations were used to demonstrate the presence of through-space (TS) conjugation in 3. Furthermore, host-guest complex formation between 3D (n = 3) and tetracyanoquinodimethane in the solid state was revealed.

Conformational, Host, and Vibrational Effects Giving Rise to Dynamic TADF Behavior in the Through-Space Charge Transfer, Triptycene Bridged Acridine-Triazine Donor Acceptor TADF Molecule TpAT-tFFO.

We present a joint experimental and theoretical study of the through-space charge transfer (CT) TADF molecule TpAT-tFFO. The measured fluorescence has a singular Gaussian line shape but two decay components, coming from two distinct molecular CT conformers, energetically only 20 meV apart. We determined the intersystem crossing rate (1 × 107 s-1) to be 1 order of magnitude faster than radiative decay, and prompt emission (PF) is therefore quenched within 30 ns, leaving delayed fluorescence (DF) observable from 30 ns onward as the measured reverse intersystem crossing (rISC) rate is >1 × 106 s-1, yielding a DF/PF ratio >98%. Time-resolved emission spectra measured between 30 ns and 900 ms in films show no change in the spectral band shape, but between 50 and 400 ms, we observe a ca. 65 meV red shift of the emission, ascribed to the DF to phosphorescence transition, with the phosphorescence (lifetime >1 s) emanating from the lowest 3CT state. A host-independent thermal activation energy of 16 meV is found, indicating that small-amplitude vibrational motions (∼140 cm-1) of the donor with respect to the acceptor dominate rISC. TpAT-tFFO photophysics is dynamic, and these vibrational motions drive the molecule between maximal rISC rate and high radiative decay configurations so that the molecule can be thought to be "self-optimizing" for the best TADF performance.

A Donor-Acceptor 10-Cycloparaphenylene and Its Use as an Emitter in an Organic Light-Emitting Diode.

Here, we explored the possibility of using cycloparaphenylenes (CPP) within a donor-acceptor TADF emitter design. 4PXZPh-[10]CPP contains four electron-donating moieties connected to a [10]CPP. In the 15 wt % doped in CzSi film, 4PXZPh-[10]CPP showed sky-blue emission with λPL = 475 nm, ΦPL = 29%, and triexponential emission decays with τPL of 4.4, 46.3, and 907.8 ns. Solution-processed OLEDs using 4PXZPh-[10]CPP exhibited sky-blue emission with an λEL of 465 nm and an EQEmax of 1.0%.

Imidazole Acceptor for Both Vacuum-Processable and Solution-Processable Efficient Blue Thermally Activated Delayed Fluorescence.

The members of the imidazole family have been widely used for electron transporting, host, conventional fluorescent, and phosphorescent materials. Although the imidazole core also has great potential as an acceptor segment of deep-blue thermally activated delayed fluorescence (TADF) owing to its high triplet energy, the emission color of imidazole-based TADF organic light-emitting diodes (OLEDs) has so far been limited to blue to green. In this work, four acridan-imidazole systems are theoretically designed aiming for deep- or pure-blue emitters. All four emitters exhibit deep-blue to blue emission owing to the high energy levels of the lowest excited singlet states, exhibiting y coordinates of Commission Internationale de l'Eclairage coordinates between 0.06 and 0.26. The molecule composed of a trifluoromethyl-substituted benzimidazole acceptor in combination with a tetramethyl-9,10-dihydroacridine donor (named MAc-FBI) achieves a high maximum external quantum efficiency (EQEMAX) of 13.7% in its application to vacuum-processed OLEDs. The emitter has high solubility even in ecofriendly nonhalogenated solvents, which motivates us to fabricate solution-processed MAc-FBI-based OLEDs, resulting in an even higher EQEMAX of 16.1%.

Effect of a twin-emitter design strategy on a previously reported thermally activated delayed fluorescence organic light-emitting diode.

In this work we showcase the emitter DICzTRZ in which we employed a twin-emitter design of our previously reported material, ICzTRZ. This new system presented a red-shifted emission at 488 nm compared to that of ICzTRZ at 475 nm and showed a comparable photoluminescence quantum yield of 57.1% in a 20 wt % CzSi film versus 63.3% for ICzTRZ. The emitter was then incorporated within a solution-processed organic light-emitting diode that showed a maximum external quantum efficiency of 8.4%, with Commission Internationale de l'Éclairage coordinate of (0.22, 0.47), at 1 mA cm-2.

Multichromophore Molecular Design for Thermally Activated Delayed-Fluorescence Emitters with Near-Unity Photoluminescence Quantum Yields.

Three multichromophore thermally activated delayed fluorescence (TADF) molecules, p-di2CzPN, m-di2CzPN, and 1,3,5-tri2CzPN, were synthesized and characterized. These molecules were designed by connecting the TADF moiety 4,5-di(9H-carbazol-9-yl)phthalonitrile (2CzPN) to different positions of a central benzene ring scaffold. Three highly soluble emitters all exhibited near-quantitative photoluminescence quantum yields (ΦPL) in toluene. High ΦPLs were also achieved in doped films, 59 and 70% for p-di2CzPN and m-di2CzPN in 10 wt % DPEPO doped film, respectively, and 54% for 1,3,5-tri2CzPN in 20 wt % doped CBP films. The rate constant of reverse intersystem crossing (kRISC) for p-di2CzPN and m-di2CzPN in DPEPO films reached 1.1 × 105 and 0.7 × 105 s-1, respectively, and kRISC for 1,3,5-tri2CzPN in the CBP film reached 1.7 × 105 s-1. A solution-processed organic light-emitting diode based on 1,3,5-tri2CzPN exhibited a sky-blue emission with CIE coordinates of (0.22, 0.44) and achieved a maximum external quantum efficiency of 7.1%.

Conformation Control of Iminodibenzyl-Based Thermally Activated Delayed Fluorescence Material by Tilted Face-to-Face Alignment With Optimal Distance (tFFO) Design.

In organic light-emitting diodes (OLEDs), all triplet excitons can be harvested as light via reverse intersystem crossing (RISC) based on thermally activated delayed fluorescence (TADF) emitters. To realize efficient TADF, RISC should be fast. Thus, to accomplish rapid RISC, in the present study, a novel TADF emitter, namely, TpIBT-tFFO, was reported. TpIBT-tFFO was compared with IB-TRZ, which contains the same electron donor and acceptor segments, specifically iminodibenzyl and triazine moieties. TpIBT-tFFO is based on a recently proposed molecular design strategy called tilted face-to-face alignment with optimal distance (tFFO), whereas IB-TRZ is a conventional through-bond type molecule. According to quantum chemical calculations, a very large RISC rate constant, k RISC, was expected for TpIBT-tFFO because not only the lowest triplet state but also the second lowest triplet state were close to the lowest excited singlet state, as designed in the tFFO strategy. IB-TRZ has two different conformers, leading to dual emission. Conversely, owing to excellent packing, the conformation was fixed to one in the tFFO system, resulting in single-peaked emission for TpIBT-tFFO. TpIBT-tFFO displayed TADF type behavior and afforded higher photoluminescence quantum yield (PLQY) compared to IB-TRZ. The k RISC of TpIBT-tFFO was determined at 6.9 × 106 s-1, which is one of the highest values among molecules composed of only H, C, and N atoms. The external quantum efficiency of the TpIBT-tFFO-based OLED was much higher than that of the IB-TRZ-based one. The present study confirms the effectiveness of the tFFO design to realize rapid RISC. The tFFO-based emitters were found to exhibit an additional feature, enabling the control of the molecular conformations of the donor and/or acceptor segments.