Through-space Charge Transfer Research Articles

A Facile One-Step Self-Assembly Strategy for Novel Carbon Dots Supramolecular Crystals with Ultralong Phosphorescence Controlled by NH4.

A new methodological design is proposed for carbon dots (CDs)-based crystallization-induced phosphorescence (CIP) materials via one-step self-assembled packaging controlled by NH4 +. O-phenylenediamine (o-PD) as a nitrogen/carbon source and the ammonium salts as oxidants are used to obtain CDs supramolecular crystals with a well-defined staircase-like morphology, pink fluorescence and ultralong green room-temperature phosphorescence (RTP) (733.56ms) that is the first highest value for CDs-based CIP materials using pure nitrogen/carbon source by one-step packaging. Wherein, NH4 + and o-PD-derived oxidative polymers are prerequisites for self-assembled crystallization so as to receive the ultralong RTP. Density functional theory calculation indicates that NH4 + tends to anchor to the dimer on the surface state of CDs and guides CDs to cross-arrange in an X-type stacking mode, leading to the spatially separated frontier orbitals and the through-space charge transfer (TSCT) excited state in turn. Such a self-assembled mode contributes to both the small singlet-triplet energy gap (ΔEST) and the fast inter-system crossing (ISC) process that is directly related to ultralong RTP. This work not only proposes a new strategy to prepare CDs-based CIP materials in one step but also reveals the potential for the self-assembled behavior controlled by NH4 +.

Linearly Arranged Multi-π-Stacked Structure for Efficient Through-Space Charge-Transfer Emitters.

Noncovalent spatial interaction has become an intriguing and important tool for constructing optoelectronic molecules. In this study, we linearly attached three conjugated units in a multi π-stacked manner by using just one trident bridge based on indeno[2,1-b]fluorene. To achieve this structure, we improved the synthetic approach through double C-H activation, significantly simplifying the preparation process. Due to the proximity of the C10, C11, and C12 sites in indeno[2,1-b]fluorene, we derived two novel donor|acceptor|donor (D|A|D) type molecules, 2DMB and 2DMFB, which exhibited closely packed intramolecular stacking, enabling efficient through-space charge transfer. This molecular construction is particularly suitable for developing high-performance thermally activated delayed fluorescence materials. With donor(s) and acceptor(s) constrained and separated within this spatially rigid structure, elevated radiative transition rates, and high photoluminescence quantum yields were achieved. Organic light-emitting diodes incorporating 2DMB and 2DMFB demonstrated superior efficiency, achieving maximum external quantum efficiencies of 28.6% and 16.2%, respectively.

Intramolecular exciplex featuring a bis-sp3 C-locked acceptor-donor-acceptor sandwich.

Intramolecular exciplex systems featuring thermally activated delayed fluorescence (TADF) have garnered significant attention in the realm of organic light-emitting diodes (OLEDs). Nonetheless, the occurrence of organic sandwich intramolecular exciplexes remains rare due to structural limitations and synthetic challenges. Herein, we present a novel rigid acceptor-donor-acceptor (A-D-A) sandwich complex, dSFQP, characterized by two sp3 C-locking moieties. This compound exhibits TADF characteristics facilitated by a multiple through-space charge-transfer process. X-ray crystallographic analysis confirms the distinctive sandwich configuration. The parallel spatial arrangement and minimized A-D-A configuration enhance electronic interactions, resulting in a high photoluminescence quantum yield, rapid reverse intersystem crossing rate, and sluggish nonradiative decay rate. OLEDs employing dSFQP as the dopant achieve a maximum external quantum efficiency (EQE) of 28.5% with a low efficiency roll-off of merely 2.8% at 1000 cd m-2. Even at a high brightness of 10 000 cd m-2, the EQE remains notably high at 17.5%. Our current results provide an effective way to further innovate the design of new organic charge-transfer complexes.

Tandem Four-Component Reaction to Access Fused Polycycles Exhibiting Aggregation-Enhanced Through-Space Charge Transfer Emission.

Rapid construction of new fluorescence emitters is essential in advancing synthetic luminescent materials. This study illustrated a piperidine-promoted reaction of chiral dialdehyde with benzoylacetonitrile and malonitrile, leading to the formation of the 6/6/7 fused cyclic product in good yield. The proposed reaction mechanism involves a dual condensation/cyclization process, achieving the formation of up to six bonds for fused polycycles. The single crystal structure analysis revealed that the fused cyclic skeleton contains face-to-face naphthyl and cyanoalkenyl motifs, which act as the electronic donor and acceptor, respectively, potentially resulting in through-space charge transfer (TSCT) emission. While the TSCT emissions were weak in solution, a notable increase in luminescence intensity was observed upon aggregation, indicating bright fluorescent light. A series of theoretical analyses further supported the possibility of spatial electronic communication based on frontier molecular orbitals, the distance of charge transfer, and reduced density gradient analysis. This work not only provides guidance for the one-step synthesis of complex polycycles, but also offers valuable insights into the design of aggregation-enhanced TSCT emission materials.

Achieving Deep‐Blue Through‐Space Charge‐Transfer Emitter by Designing the Donor‐π‐Donor‐σ‐Acceptor Molecular Structure

AbstractIn the realm of organic light‐emitting diode (OLED), through‐space charge transfer (TSCT) thermally activated delayed fluorescence (TADF) emitters have demonstrated remarkable achievements. Nevertheless, realizing both deep‐blue emission and high efficiency by the TSCT strategy remains a persistent challenge. Here, the novel donor‐π‐donor‐σ‐acceptor (D‐π‐D‐σ‐A) type deep‐blue TSCT emitter, namely D‐tCz‐BO, is formulated to investigate its performance in OLED. D‐tCz‐BO show a narrow deep‐blue emission and efficient TADF character (λPL = 448, FWHM = 54 nm, ΦPL = 82%, and ΔEST = 0.09 eV). More importantly, the OLED based on D‐tCz‐BO as the emitter showed a maximum external quantum efficiency (EQEmax) of 20.5%, with a Commission Internationale de l'Eclairage (CIE) coordinate of (0.14, 0.12). This represents one of the best deep‐blue TSCT‐TADF emitters to date.

Theoretical insights into long-range coupling of electron-hole pairs in TCTA–PO-T2T exciplex

This work reports theoretical investigations concerning long-range coupling of electron-hole pairs in spatially separated exciplex (SSE) systems via Density Functional Theory and Time-Dependent Density Functional Theory. Based on TCTA−PO-T2T parent exciplex, where 4,4′,4″-Tris(carbazol-9-yl)triphenylamine (TCTA) serves as donor (D) and 2,4,6-Tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T) as acceptor (A), SSEs are constructed by intentionally tuning the D−A distance. The calculation results demonstrate that all SSEs, even if the D−A distance is over 14 Å, exhibit the clear and strong charge transfer character in terms of DCT, qCT, and t indexes. As the D−A distance increases, the energy gap of SSEs is increased, resulting in the blueshift of emission spectra. Calculation and experiment results show a good consistency, indicating that our model could well describe SSEs. Meanwhile, the reduced energy gap between CT and 3LE and more degenerate states could boost reverse intersystem crossing via vibronic coupling and hyperfine coupling, eventually improving the electroluminescent performance of SSEs. Our study suggests that manipulation of relative energy alignment via controlling D−A distance not only promotes the properties of exciplexes, but also offers guidance for designing thermally activated delayed fluorescence emitters through-space charge transfer.

Face-to-face π-π interactions and electron communication boosting efficient reverse intersystem crossing in through-space charge transfer molecules

Face-to-face π-π interactions and electron communication boosting efficient reverse intersystem crossing in through-space charge transfer molecules

Guest‐Induced Thermally Activated Delayed Fluorescence Organic Supramolcular Macrocycle Scintillators for High‐Resolution X‐Ray Imaging

AbstractOrganic scintillators, pivotal in security and medical applications, face challenges due to limited X‐ray absorption and exciton utilization. Herein, a novel class of organic scintillators is introduced, named guest‐induced thermally activated delayed fluorescence (TADF) within supramolecular macrocycles via host‐guest through‐space charge transfer (TSCT). Four co‐crystals are obtained through orthogonal crystallizations involving calix[3]acridan (C[3]A) and calix[3]phenothiazine (C[3]P) macrocycles as hosts, along with 1,2‐dicyanobenzene (DCB) and 4‐bromo‐1,2‐benzenedicarbonitrile (BrDCB) as guests. Interestingly, DCB@C[3]A and BrDCB@C[3]A co‐crystals exhibit strong host‐guest TSCT with reduced single‐triplet energy gap for efficient TADF emission, which leads to enhanced exciton utilization and X‐ray absorption, yielding radioluminescence intensities over 29 and 25 times higher than C[3]A. Similarly, substituting C[3]A with C[3]P, the obtained TADF co‐crystals also outperform C[3]P in scintillation performance. Additionally, the scintillation color of co‐crystals can be adjusted by varying the electron‐donating abilities of macrocycles and the electron‐accepting abilities of guests, offering a simpler color‐tuning mechanism than covalent‐bonded scintillators. Furthermore, the flexible film based on DCB@C[3]A exhibits promising application in X‐ray radiography, showcasing a high spatial resolution of 20 lp mm−1 @MTF = 0.77. The innovative strategy of fabricating organic scintillators via reversible non‐covalent interactions presents a novel solution for designing color‐tunable and high‐performance scintillators.

Enhancing Light-Emitting Efficiency of Blue Through-Space Charge Transfer Emitters via Fixing Configuration Induced by Intramolecular Hydrogen Bonding.

Closely aligned configuration of the donor (D) and acceptor (A) is crucial for the light-emitting efficiency of thermally activated delayed fluorescence (TADF) materials with through-space charge transfer (TSCT) characteristics. However, precisely controlling the D-A distance of blue TSCT-TADF emitters is still challenging. Herein, an extra donor (D*) located on the side of the primary donor (D) is introduced to construct the hydrogen bonding with A and thus modulate the distance of D and A units to prepare high-efficiency blue TSCT emitters. The obtained "V"-shaped TSCT emitter presents a minimal D-A distance of 2.890 Å with a highly parallel D-A configuration. As a result, a high rate of radiative decay (>107 s-1) and photoluminescence quantum yield (nearly 90%) are achieved. The corresponding blue organic light-emitting diodes show maximum external quantum efficiencies (EQEmax) of 27.9% with a Commission Internationale de L'Eclairage (CIE) coordinate of (0.16, 0.21), which is the highest device efficiency of fluorene-based blue TSCT-TADF emitters. In addition, the TSCT-TADF emitter-sensitized OLEDs also achieve a high EQEmax of 29.3% with a CIE coordinate of (0.12, 0.16) and a narrow emission.

Intramolecular Through-Space Charge Transfer in Compact Cofacial Thermally Activated Delayed Fluorescence Emitters

Intramolecular Through-Space Charge Transfer in Compact Cofacial Thermally Activated Delayed Fluorescence Emitters

Strategic Insertion of Heavy Atom to Tailor TADF OLED Material for the Development of Type I Photosensitizing Catalytic Red Emissive Assemblies.

The work presented in the manuscript describes a simple strategy for transforming thermally activated delayed fluorescent organic light-emitting diodes (TADF OLEDs) compound 10-(dibenzo[a,c]phenazin-11-yl)-10H-phenoxazine (DPZ-PXZ) into type I photosensitizer 10-(dibenzo[a,c]phenazin-11-yl)-10H-phenothiazine (DPZ-PHZ) by strategically introducing sulfur atom in the photosensitizing core. The synthesized compound DPZ-PHZ exhibits aggregation-induced enhancement (AIE) and through-space charge transfer (TSCT) characteristics and generates red emissive assemblies in mixed aqueous media. The original compound DPZ-PXZ exhibits well-separated HOMO and LUMO levels and is reported to have highly efficient reverse intersystem crossing (RISC). In comparison, the incorporation of sulfur atom in the phenothiazine donor regulates the electronic communication between donor and acceptor units and promotes the intersystem crossing (ISC) in DPZ-PHZ molecules. Interestingly, compound DPZ-PHZ exhibits rapid activation of aerial oxygen for instant generation of superoxide radical anion. Backed by excellent type I photosensitizing activity, DPZ-PHZ assemblies have high catalytic potential for the synthesis of benzimidazoles, benzothiazoles and quinazolines derivatives under mild reaction conditions. The work presented in the manuscript provides an insight into the combination of heavy atom approach and TSCT for achieving adequate electronic communication between donor and acceptor units, balanced RISC/ISC, and stabilized-charge separated state for the development of efficient type I photosensitizing assemblies.

Copper(I) TADF exciplexes via Metal-Perturbed Through-Space charge transfer for efficient OLEDs

Organo-copper(I) emitters are promising cost-effective candidates as triplet-harvesting dopants in organic light-emitting diodes (OLEDs). To date, the mainstream design of Cu(I) emitters depends on ligand engineering to modify intramolecular charge transfer and thus modulate the related optoelectronic properties. However, little is known on luminescent Cu(I) systems based on intermolecular charge transfer. For the first time, the proof-of-concept Cu(I) exciplexes were developed employing a triazine-containing molecule DMIC-TRZ as an acceptor and several Cu(I)-based carbene-metal-amide (CMA) complexes as donors. The formation of these exciplexes is strongly associated with d-orbital participation of Cu atom on the highest occupied molecular orbital of CMA complexes to match with the acceptor DMIC-TRZ. These Cu(I) exciplexes not only displayed donor-dependent emission colors spanning from sky blue to red but also exhibited distinct thermally activated delayed fluorescence (TADF) via copper(I)-perturbed through-space charge transfer (TSCT). The OLEDs adopting the Cu(I) exciplexes as emitters delivered good external quantum efficiency (EQE) of up to 10.9%. Furthermore, the use of these Cu(I) exciplexes as hosts for multi-resonance TADF emitters delivered narrowband electroluminescence with high EQEs of up to 24.9%, superior to the reference OLEDs based on the common host.

Regulation for photophysical properties of thermally activated delayed fluorescence molecules with through-space charge transfer by substitution effect

Thermally activated delayed fluorescence (TADF) molecules with through-space charge transfer (TSCT) have attracted much attention in recent years. The photophysical properties of four TADF molecules with TSCT properties were studied in toluene and in solid phase. Our calculation results indicate that ortho substitution and fluorine substitution not only favor the generation of TADF, but also promote room temperature phosphorescence in solid phase. The results provide deeper understanding of substitution effect on light-emitting properties of TSCT-TADF emitters and may favor the design of TADF emitters.

Through-Space Charge-Transfer Organogold(III) Complexes Enable High-Performance X-ray Scintillation and Imaging.

Organic scintillators have recently attracted growing attention for X-ray detection in industrial and medical applications. However, these materials still face critical obstacles of low attenuation efficiency and/or inefficient triplet exciton utilization. Here we developed a new category of organogold(III) complexes, Tp-Au-1 and Tp-Au-2, through adopting a through-space interaction motif to realize high X-ray attenuation efficiency and efficient harvesting of triplet excitons for emission. Thanks to the efficient through-space charge transfer process, this panel of complexes achieved higher photoluminescence quantum yield and shorter radiative lifetimes compared with the through-bond reference complexes. Inspiringly, these organogold(III) complexes exhibited polarity-dependent emission origins: thermally activated delayed fluorescence and/or phosphorescence. Under X-ray irradiation, Tp-Au-2 manifested intense radioluminescence together with a record-high scintillation light yield of 77,600 photons MeV-1 for organic scintillators. The resulting scintillator screens demonstrated high-quality X-ray imaging with >16.0 line pairs mm-1 spatial resolution, outstripping most organic and inorganic scintillators. This finding provides a feasible strategy for the design of superior organic X-ray scintillators.

Dynamic Reversible Full‐Color Piezochromic Fluorogens Featuring Through‐Space Charge‐Transfer Thermally Activated Delayed Fluorescence and their Application as X‐Ray Imaging Scintillators

AbstractThermally activated delayed fluorescence (TADF) emitters featuring through‐space charge transfer (TSCT) can be excellent candidates for piezochromic luminescent (PCL) materials due to their structural dynamics. Spatial donor‐acceptor (D−A) stacking arrangements enable the modulation of inter‐ and intramolecular D−A interactions, as well as spatial charge transfer states, under varying pressure conditions. Herein, we demonstrate an effective approach toward dynamic reversible full‐color PCL materials with TSCT‐TADF characteristics. Their single crystals exhibit a full‐color‐gamut PCL process spanning a range of 170 nm. Moreover, the TSCT‐TADF‐PCL emitters display a unity photoluminescence quantum yield, and show promising application in X‐ray scintillator imaging.

Dynamic Reversible Full-Color Piezochromic Fluorogens Featuring Through-Space Charge-Transfer Thermally Activated Delayed Fluorescence and their Application as X-Ray Imaging Scintillators.

Thermally activated delayed fluorescence (TADF) emitters featuring through-space charge transfer (TSCT) can be excellent candidates for piezochromic luminescent (PCL) materials due to their structural dynamics. Spatial donor-acceptor (D-A) stacking arrangements enable the modulation of inter- and intramolecular D-A interactions, as well as spatial charge transfer states, under varying pressure conditions. Herein, we demonstrate an effective approach toward dynamic reversible full-color PCL materials with TSCT-TADF characteristics. Their single crystals exhibit a full-color-gamut PCL process spanning a range of 170 nm. Moreover, the TSCT-TADF-PCL emitters display a unity photoluminescence quantum yield, and show promising application in X-ray scintillator imaging.

Room-Temperature Phosphorescence Materials Featuring Triplet Hybrid Local Charge Transfer Emission.

Room-temperature phosphorescence materials have found important applications in dissolved oxygen sensing, temperature monitoring, anticounterfeiting, etc., because of their prolonged phosphorescence lifetime. However, the known systems mainly utilize the triplet local excited state emission, which is generally less sensitive to microenvironment perturbation. In this work, we designed a series of 4-phenyl-1,8-naphthalimide (NMI) derivatives containing different numbers of carbazole (Cz) units (denoted as NMI-Cz, NMI-2Cz, and NMI-3Cz). Steady state and time-resolved spectroscopy studies determined that the compounds undergo intramolecular through-space charge transfer in solution, yielding a triplet hybrid local charge transfer state. Room-temperature phosphorescence emission was observed in compound-doped poly(methyl methacrylate) thin films upon ammonia treatment. Interestingly, emission from different films exhibited different persistence times. We believe a film-based, time-resolved luminescent ammonia sensor could be developed by making a device of the emissive films as fabricated.

Through-Space Charge-Transfer-Based Aggregation-Induced Emission and Thermally Activated Delayed Fluorescence in Fused 2H-Chromene Coumarin Congener Generating ROS for Antiviral (SARS-CoV-2) Approach.

Harvesting triplets in metal-free organic frameworks at ambient conditions and finding appropriate applications are a formidable challenge. Herein, we report a donor-acceptor-type system composed of carbazole and fused 2H-chromene coumarin derivative, exhibiting triplet harvesting thermally activated delayed fluorescence (TADF) and aggregation-induced emission (AIE) behavior in solid and aggregated states, respectively. The presence of an sp3 linker and the introduction of a selected cyano/ester group in the acceptor result in twisted D-A architectures, further assisting in the suppression of nonradiative deactivation via through-space charge transfer and H-bonding interactions, fulfilling the stringent requirements for the simultaneous process of TADF and AIE, successively. Experimental and theoretical results revealed that the participation of the singlet/triplet charge transfer (1CT/3CT) and the higher lying hybrid triplet locally excited charge-transfer state (3LE + 3CT) leads to an efficient TADF. Both of the synthesized AIE-TADF congeners actively participated in the generation of reactive oxygen species (ROS) in nanoaggregate forms and were further explored computationally for antiviral prospects as inhibitors of the SARS-CoV-2 spike protein.

Theoretical Study and Design for Thermally Activated Delayed Fluorescence Emitters with Through-Space Charge Transfer from an Acridine Derivative Donor to an O-Bridged Triphenylboron Boroxy Acceptor.

The through-space charge transfer thermally activated delayed fluorescence (TSCT-TADF) properties of a series of molecules were characterized and tested theoretically by density functional theory and time-dependent density functional theory. By analyzing the weak interaction of the molecules at the ground state and calculating the transition contribution ratio of the donor, acceptor, and bridge in the excited state, we verified the through-space charge transfer characteristic of these molecules. We designed new molecules on the basis of the reported molecules (non-TADF molecule 1 and TADF molecule 2) to improve the performance. Smaller singlet-triplet energy gaps and larger spin-orbit coupling were obtained in the designed molecules, which is beneficial to obtain higher intersystem crossing and reverse intersystem crossing rates (kRISC). In addition, we calculated the radiation rate and the singlet-triplet reorganization energy, which is used to characterize the nonradiation rate. The comprehensive evaluation of both radiative and nonradiative processes shows that molecules 4 and 6 have the potential to be highly efficient TSCT-TADF materials.

A general supramolecular strategy for fabricating full-color-tunable thermally activated delayed fluorescence materials

Developing a facile and feasible strategy to fabricate thermally activated delayed fluorescence materials exhibiting full-color tunability remains an appealing yet challenging task. In this work, a general supramolecular strategy for fabricating thermally activated delayed fluorescence materials is proposed. Consequently, a series of host–guest cocrystals are prepared by electron-donating calix[3]acridan and various electron-withdrawing guests. Owing to the through-space charge transfer mediated by multiple noncovalent interactions, these cocrystals all display efficient thermally activated delayed fluorescence. Especially, by delicately modulating the electron-withdrawing ability of the guest molecules, the emission colors of these cocrystals can be continuously tuned from blue (440 nm) to red (610 nm). Meanwhile, high photoluminescence quantum yields of up to 87% is achieved. This research not only provides an alternative and general strategy for the fabrication of thermally activated delayed fluorescence materials, but also establishes a reliable supramolecular protocol toward the design of advanced luminescent materials.