Exciplex Formation Research Articles

Guest-Mediated Modulation of Photophysical Pathways in a Coronene Bisimide Cyclophane.

The properties and functions of chromophores utilized by nature are strongly affected by the environment formed by the protein structure in the cells surrounding them. This concept is transferred here to host-guest complexes with the encapsulated guests acting as an environmental stimulus. A new cyclophane host based on coronene bisimide is presented that can encapsulate a wide variety of planar guest molecules with binding constants up to (4.29 ± 0.32) × 1010 M-1 in chloroform. Depending on the properties of the chosen guest, the excited state deactivation of the coronene bisimide chromophore can be tuned by the formation of host-guest complexes toward fluorescence, exciplex formation, charge separation, room-temperature phosphorescence (RTP), or thermally activated delayed fluorescence (TADF). The photophysical processes were investigated by UV/vis absorption, emission, and femto- and nanosecond transient absorption spectroscopy. To enhance the TADF, two different strategies were used by employing suitable guests: the reduction of the singlet-triplet gap by exciplex formation and the external heavy atom effect. Altogether, by using supramolecular host-guest complexation, a versatile multimodal chromophore system is achieved with the coronene bisimide cyclophane.

Gold Nanoparticles Modulate Excimer and Exciplex Dynamics of PDDCP-Conjugated Polymers.

How plasmonic nanostructures modulate the behavior of exciplexes and excimers within materials remains unclear. Thus, advanced knowledge is essential to bridge this gap for the development of optoelectronic devices that leverage the interplay between plasmonic and conjugated polymer hybrid materials. Herein, this work aims to explore the role of gold nanoparticles (AuNPs) in modulating exciplex and excimer states within the conjugated polymer poly(2,5-di(3,7-dimethyloctyloxy) cyanoterephthalylidene) (PDDCP), known for its photoluminescent and semi-conductive properties, aiming to create innovative composite materials with tailored optical features. The spectral analysis was conducted to investigate the effects of AuNPs on the PDDCP, varying AuNP volume percentages to measure changes in the absorption profile, molar extinction coefficient (ε), absorption cross-section (σa), and optical bandgap (Eg). Fluorescence spectra of the mixture at different volume ratios were also examined to assess exciplex formation, while amplified spontaneous emission (ASE) profiles were analyzed to study the behavior and photochemical stability of the polymer-NP hybrid material. Increasing AuNP volume induced both blue and red shifts in the absorption profile of the PDDCP. Higher AuNPs concentrations correlated with decreased ε and σa, inversely impacting Eg. The emission spectra obtained at varied AuNP volume ratios indicated significantly enhanced exciplex and excimer formations. The ASE profiles remained consistent but showed reduced intensity with increasing AuNPs concentrations, indicating their influence on hybrid material behavior and stability. The findings suggest that AuNPs affect PDDCP's optical characteristics, altering the absorption profile, bandgap, and fluorescence spectra. Furthermore, the observed reduction in ASE intensity highlights their influence on the behavior and photochemical stability of the hybrid material. These results contribute to a better understanding of the versatile applications of plasmonic-conjugated hybrid polymers.

Exciplex, Not Heavy-Atom Effect, Controls the Triplet Dynamics of a Series of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules.

The 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 12H-benzo[4,5]thieno[2,3-a]carbazole and dicyanopyridine is compared with their nonsulfur control molecules designed to probe such SOC effects. We reveal that unexpected intermolecular interactions of the D-A molecules with carbazole-containing host materials instead serve as the dominant pathway for triplet decay kinetics in these materials. In-depth photophysical and computational studies combined with organic light emitting diode measurements demonstrate that the anticipated heavy-atom effect from sulfur is overshadowed by exciplex formation. Indeed, even the unsubstituted acceptor fragments exhibit pronounced TADF exciplex emission in appropriate carbazole hosts. The intermolecular charge transfer and TADF in these systems are further confirmed by detailed time-dependent density functional theory studies. This work demonstrates that anticipated heavy-atom effects in TADF emitters do not always control or even impact the photophysical and electroluminescence properties.

Small-Molecule:Polymer Composites for Transparent Films with Visible Emission.

The analysis of the shift in photoluminescence emission for a blend of polyvinylcarbazole and acrylonitrile derivative compounds is reported. The small-molecule compounds have different functional groups, phenyl, pyridine, or methyl phenyl, attached to an acrylonitrile group. According to the functional group, the blue emission for pure dye shifts to green or yellowish in the blend film. Several PVK:dye ratios from 0:100 to 20:80 were used for film deposition. The film morphology was analyzed by atomic force microscopy; for low dye content, homogeneous films were achieved. However, aggregates of several micrometers are formed on the surface of films with higher dye concentrations. The shift in emission occurs only with PVK, and for a non-conjugated matrix such as polystyrene, the emission remains unchanged. The interaction of dyes with PVK leading to change in emission was also achieved by grinding dye and polymer. Results showed that shifts in emission could come from exciplex formation along with changes in dye intermolecular interactions. The blend films were highly transparent in the visible spectra due to the absorption in the UV region for dye and matrix. The films with ratio PVK: dye ratio 80:20 was used as active layer in OLEDs.

N-Perfluorooctane versus n-Octane: Pyrene Fluorescence to Compare and Contrast Solute Solvation.

Fluorous solvents may offer distinctly different solvation environments to a solute compared to their hydrocarbon analogues due to the inherently high electronegativity associated with fluorine. Solute solvation within n-perfluorooctane (PFO) is compared with that in n-octane using the well-established polycyclic aromatic hydrocarbon (PAH) fluorescence probe pyrene in the temperature range of 288 to 318 K. Both density (ρ) and dynamic viscosity (η) of PFO are considerably higher than those of n-octane. UV-vis molecular absorbance, fluorescence emission/excitation, and excited-state emission intensity decay reveal the cybotactic region of pyrene to be more nonpolar in PFO than that in n-octane. Bimolecular quenching rate constants (kq) for the pyrene-nitrobenzene fluorophore-quencher pair adhere to the Stokes-Einstein formulation; however, they are considerably higher than the estimated rate constants for the diffusion-controlled process (kdiff). This is due to the high electron affinity of nitrobenzene leading to aromatic π-π interactions between pyrene and nitrobenzene. For a nonaromatic low electron affinity quencher, such as nitromethane, while kq < kdiff in n-octane, kq > kdiff in PFO. This is due to the fact that highly electronegative fluorines on PFO stabilize the partial positive charge (δ+) that develops on excited pyrene during electron/charge transfer to the quencher nitromethane, facilitating quenching in the process. Exciplex formation between pyrene and triethylamine (TEA) is more favored in PFO as opposed to n-octane although ηPFO > ηn-octane. The developing charge on the exciplex is stabilized by the electronegative fluorines of the PFO. The pyrene-TEA exciplex appears to form exclusively in the excited state of pyrene, and the kinetics of exciplex formation is in the subnanosecond regime. On the contrary, the efficiency of exciplex formation between pyrene and N,N-dimethylaniline (DMA) is comparable in PFO and n-octane, and the kinetics is slower in comparison to that of the pyrene-TEA exciplex. Certain ground-state heterogeneity is detected for the pyrene-DMA system in PFO due to the low solubilizing ability of the fluorous solvent. Highly electronegative fluorines on perfluorohydrocarbon solvents are found to offer unusual and unique solvation characteristics.

Thermally activated delayed fluorescence dendrimers with strategic dendrons to construct highly efficient solution-processed OLEDs

For the promising merits of the precise molecular structures and the satisfactory dissolvability, Thermally activated delayed fluorescence (TADF) dendrimers are turning into the attractive candidates for fully solution-processed organic light-emitting diodes (OLEDs). However, the rational design of TADF dendrimers with strategic dendrons for improving the efficiency and decreasing efficiency roll-off is still challenging. Here, two TADF dendrimers, (4S,5R)-2,4,5,6-tetrakis(4-((6-((9-(3-(9H-carbazol-9-yl)phenyl)-9H-carbazol-3-yl)oxy)hexyl)oxy)-9H-carbazol-9-yl)isophthalonitrile (G-O-mCP) and (4S,5R)-2,4,5,6-tetrakis(4-((6-(3,5-bis(1-phenyl-1H-benzo[d]imidazol-2-yl)phenoxy)hexyl)oxy)-9H-carbazol-9-yl)isophthalonitrile (G-O-DPBi) were developed and synthesized by integrating the peripheral strategic dendrons with the emissive core through nonconjugated alkoxy chains. Impressively, the peripheral dendron of G-O-mCP possessing the superior hole-transporting capability belongs to the electron-donor category and the peripheral dendron of G-O-DPBi with the admirable electron-transporting capability belongs to the electron-acceptor category. The elaborate regulation of the different dendrons with solubilizing groups is beneficial for restraining the aggregation-caused quenching (ACQ) effect and balancing the carrier transport capability. Consequently, the fully solution-processed device based on G-O-mCP realized the maximum external quantum efficiency (EQE) of 19.98 %. In addition, the formation of the interfacial exciplex endows the solution-processed device with a extremely low turn-on voltage (Von) of 2.7 V and a high power efficiency (PE) of 43.80 lm/W, which is among the highest power efficiency of the reported TADF-OLEDs.

Unexplored Exciplex Formation by Dual Excitation of Donor and Acceptor Layers Optically and Electrically

AbstractElectron donor and acceptor interactions are the fundamentals for the emergence of optoelectronic functions in most organic devices. In particular, exciplexes, which hold the possibility to utilize dark triplets, are widely investigated in organic light‐emitting diodes. However, the relatively low radiative decay rate with a low photoluminescence quantum yield poses further advanced challenges. Traditionally, it is well recognized that exciplexes are formed through a charge transfer process, i.e., direct electron transfer, by photoexciting either a donor or an acceptor component. In this study, the focus is on a long‐range exciplex system where tris(4‐carbazoyl‐9‐ylphenyl)amine (TCTA) and 2,4,6‐tris[3‐(diphenylphosphinyl)phenyl]−1,3,5‐triazine (PO‐T2T) serve as the donor and acceptor, respectively. Moreover, 1,2‐bis(triphenylsilyl) benzene (UGH2) and bis[2‐(diphenylphosphino)phenyl]ether oxide (DPEPO), having a wide energy gap and a high triplet energy level, are employed as the double insulating layer to suppressing direct electron transfer between the donor and acceptor. The indirect through‐space exciplex formation is demonstrated by the simultaneous excitation of both donor and acceptor layers optically and electrically, providing a new route for exciplex formation.

Theoretical Study of the Exciplex Formation in an m-MTDATA–BPHEN OLED

The formation of charge-transfer (CT) exciplexes in m-MTDATA–BPhen (4,4',4''-tris[(3-methylphenyl)phenylamino]-triphenylamine)–bathophenanthroline) donor-acceptor pair is studied using density functional theory (DFT) and multireference quantum chemistry. It is shown that the lowest excited singlet S1 and one of the low-lying triplets have the CT character, while the lowest triplet is localized on the BPhen molecule, which agrees with the experimental fluorescence and phosphorescence data. A multireference treatment agrees with the DFT calculations and shows that the CT character of the exciplex states in such donor-acceptor systems is not an artifact of the functional.

Methoxylated bis(pentafluorophenyl)boron‐β‐diketonates: Synthesis, Optical Properties and Hydrolytic Stability

AbstractA series of methoxylated bis(pentafluorophenyl)boron‐β‐diketonates (dkB(C6F5)2) with intense emission has been synthesized and characterized by a variety of physicochemical methods. The photophysical properties of the synthesized compounds were thoroughly investigated by electronic absorption, steady‐state, and time‐resolved fluorescence spectroscopy in both solution and solid state. The studied compounds exhibit solvatochromic behavior attributed to the intramolecular charge transfer (ICT) nature of the first excited state. The formation of exciplexes between DBMB(C6F5)2 and benzene derivatives was also studied. Notably, the studied compounds display a complex luminescence profile in the solid state, featuring fluorescence, delayed fluorescence and phosphorescence emission. Furthermore, the hydrolytical stability of the complexes was assessed, demonstrating excellent resistance to hydrolysis. Estimated rate constants, determined at 60 °C, are significantly lower (90‐2000 times) than those observed for the well‐studied dibenzoylmethanatoboron difluoride (DBMBF2). The incorporation of pentafluorophenyl substituents at the boron atom enables the synthesis of highly fluorescent and hydrolytically stable boron chelate complexes, suitable for sensing and bioimaging applications in water‐containing environments.

Exciplex Formation by Complexation of an Electron-Accepting Guest in an Electron-Donating Pillar[5]arene Host Liquid.

We present a novel system, a liquid-state pillar[5]arene decorated with tri(ethylene oxide) chains, that brings electron-donor and electron-acceptor molecules into proximity for efficient exciplex formation. The electron-accepting guests exhibit a blue-purple emission from a localized excited state upon excitation in common solvents. However, directly dissolving the guests in the electron-donating pillar[5]arene liquid (a bulk system) results in visible green emission from the formed exciplexes. In the bulk system, the guest molecules are always surrounded by excess pillar[5]arene molecules, resulting in the formation of mainly inclusion-type exciplexes. In the bulk system, energy migration occurs between the pillar[5]arene molecules. Excitation of the pillar[5]arenes results in a more intense green exciplex emission than that observed upon direct excitation of the guests. In summary, the pillar[5]arene liquid is a novel system for achieving efficient exciplex formation and energy migration that is different from typical solvent and solid systems.

Effective exciplex host for solution-processed narrowband blue TADF-OLEDs using a 9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole analogue with an adamantane substituent

Implementing an exciplex host system in the emitting layer is crucial for achieving highly efficient thermally activated delayed fluorescence (TADF) and phosphorescent organic light-emitting diodes (OLEDs). In this study, we successfully designed and synthesized 3-((3r,5r,7r)-adamantan-1-yl)-9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole (AdCz-DBT) and 9-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole (Cz-DBT) as p-type hosts for the exciplex host implementation, and 7-(4-(tert-butyl)phenyl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene (tPDBA) as an n-type host. The AdCz-DBT host incorporates a large and robust adamantane group into Cz-DBT, increasing molecular weight, film-forming properties and thermal stability. Additionally, AdCz-DBT maintains energy levels and photophysical properties similar to those of adamantane-free Cz-DBT. Efficient exciplex emission was observed in the blend film due to well-matched energy levels of the synthesized p- and n-type hosts. The introduction of adamantane into Cz-DBT did not hinder exciplex formation, resulting in a relatively high photoluminescence quantum yield and improved charge balance in the mixed host with tPDBA.Ultimately, the solution-processed blue TADF-OLED with the AdCz-DBT:tPDBA blend host demonstrated a relatively high external quantum efficiency of 8.00% and a long operational lifetime, exhibiting excellent performance compared to devices using the Cz-DBT:tPDBA blend host.

Highly Efficient Blue Fluorescent Organic Light-Emitting Devices Based on λ5-Phosphinine Derivatives.

Although λ5-phosphinine derivatives are known as a promising class of blue fluorescent emitters, those photoluminescent quantum yield (PLQY) values have been reached up to 92 %, however, only a few examples have been explored as an emitter for blue organic light-emitting device (OLED), and the external quantum efficiency (EQE) has been below 2.4 % so far. In this study, we newly developed two types of blue λ5-phosphinine derivatives namely CN-COCF3 and CO2Me-CHO, and investigated the photophysical properties in the solid states. The photophysical analyses in solid state films suggested that the strong electron-accepting nature of these λ5-phosphinine derivatives caused the inferior PLQY values, and the exciplex formation with the host and neighboring materials should be avoided to improve the device efficiency. By choosing suitable host and neighboring materials with deep ionization potentials, we successfully realized efficient blue fluorescent OLEDs with EQE of over 4 % and CIE (0.14, 0.18). This is among the best in λ5-phosphinine-based blue OLEDs so far.

High‐Efficiency Near‐Infrared OLED Enabled by Exciplex‐Forming Hosts and a New Organic Fluorescent Emitter

AbstractTwo blends comprising new dicyanopyrazine‐based acceptors (m‐CN and p‐CN) and a carbazole‐based donor CPTBF are explored for exciplex formation. The CPTBF:m‐CN and CPTBF:p‐CN blends show the signature red‐shifted emission together with the delayed fluorescence observed in time‐resolved measurement, manifesting the characteristics of thermally activated delayed fluorescence (TADF). The electroluminescence (EL) device employing CPTBF:m‐CN (CPTBF:p‐CN) blend as the emitting layer (EML) achieved an EQE of 5.22% (2.05%) with the EL λmax centered at 607 nm (625 nm). The exciplex excitons can be efficiently extracted by a new benzobisthiadiazole‐based near‐infrared (NIR) emitter DCzPBBT, where a device is configured with CPTBF:m‐CN: (5 wt.%) DCzPBBT as the EML to achieve a high EQE of 5.32% and an EL λmax 758 nm. Further increase of the doping concentration to 10 wt.% of DCzPBBT exhibits a bathochromic shifted EL λmax to 772 nm with 94% spectral coverage in the NIR (&gt;700 nm) region, while the device EQE retains at 4.06%. The superior device performance stems from the highly efficient energy transfer between the exciplex‐forming host and NIR dopant together.

Exciplex-forming cohost systems with 2,7-dicyanofluorene acceptors for high efficiency red and deep-red OLEDs

Two 2,7-dicyaonfluorene-based molecules 27-DCN and 27-tDCN are utilized as acceptors (A) to combine with hexaphenylbenzene-centered donors (D) TATT and DDT-HPB for probing the exciplex formation. The photophysical characteristics reveal that the steric hindered 27-tDCN not only can increase the distance of D and A, resulting in a hypsochromic emission, but also dilute the concentration of triplet excitons to suppress non-radiative process. The 27-tDCN-based exciplex-forming blends exhibit better photoluminescence quantum yield (PLQY) as compared to those of 27-DCN-based pairs. In consequence, among these D:A blends, the device employing DDT-HPB:27-tDCN blend as the emissiom layer (EML) exhibits the best EQE of 3.0% with electroluminescence (EL) λmax of 542 nm. To further utilize the exciton electrically generated in exciplex-forming system, two D–A–D-configurated fluorescence emitter DTPNT and DTPNBT are doped into the DDT-HPB:27-tDCN blend. The nice spectral overlap ensures fast and efficient Förster energy transfer (FRET) process between the exciplex-forming host and the fluorescent quests. The red device adopting DDT-HPB:27-tDCN:10 wt% DTPNT as the EML gives EL λmax of 660 nm and maximum external quantum efficiency (EQEmax) of 5.8%, while EL λmax of 685 nm and EQE of 5.0% for the EML of DDT-HPB:27-tDCN:10 wt% DTPNBT. This work manifests a potential strategy to achieve high efficiency red and deep red OLED devices by incorporating the highly fluorescent emitters to extract the excitons generated by the exciplex-forming blend with bulky acceptor for suppressing non-radiative process.

Nanosecond Laser Flash Photolysis Study of the Photochemistry of 2‑Alkoxy Thioxanthones

Laser flash photolysis studies (l = 355 nm) on the characterization and reactivity for the triplet excited state of 2-methoxythioxanthone, 2-benzyloxythioxanthone, and 2-(n-propoxy) thioxanthone revealed that the transients generated in their excitation, in acetonitrile, have absorption bands with maxima at 310 and 620 nm. These transients decayed by a mixed 1st and 2nd order kinetics, with a lifetime of 5.3 ms for 2-methoxythioxanthone and benzyloxythioxanthone and 3.9 ms for 2-(n-propoxy) thioxanthone. In methanol, ethanol, and 2-propanol, a new absorption at 430-460 nm was observed, which was attributed to their corresponding ketyl radical (the second-order quenching rate constant (kq) is ca. 105 L mol-1 s-1). The energy transfer rate constants for trans-stilbene, 1-methylnaphthalene, and 1,3-cyclohexadiene were diffusion-controlled, indicating a triplet energy for these alkoxy thioxanthones higher than 61 kcal mol-1. The quenching rate constant observed for 1,4-cyclohexadiene (ca.109 L mol-1 s-1) suggests that the lowest energy triplet excited state for these thioxanthones must have nπ* character. For phenols and indole (kq ca. 109 L mol-1 s-1), the reaction mechanism must involve the initial formation of a triplet exciplex, followed by a coupled electron/proton transfer. For triethylamine and 1,4-diazabicyclo[2.2.2]octane (kq ca. 109 L mol-1 s-1) it was observed the formation of the radical anion of the alkoxy thioxanthones formed from electron transfer (l = 410 nm).

Blue emitting exciplex for yellow and white organic light-emitting diodes

White organic light-emitting diodes (WOLEDs) have several desirable features, but their commercialization is hindered by the poor stability of blue light emitters and high production costs due to complicated device structures. Herein, we investigate a standard blue emitting hole transporting material (HTM) N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine (NPB) and its exciplex emission upon combining with a suitable electron transporting material (ETM), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ). Blue and yellow OLEDs with simple device structures are developed by using a blend layer, NPB:TAZ, as a blue emitter as well as a host for yellow phosphorescent dopant iridium (III) bis(4-phenylthieno[3,2-c]pyridinato-N,C2')acetylacetonate (PO-01). Strategic device design then exploits the ambipolar charge transport properties of tetracene as a spacer layer to connect these blue and yellow emitting units. The tetracene-linked device demonstrates more promising results compared to those using a conventional charge generation layer (CGL). Judicious choice of the spacer prevents exciton diffusion from the blue emitter unit, yet facilitates charge carrier transport to the yellow emitter unit to enable additional exciplex formation. This complementary behavior of the spacer improves the blue emission properties concomitantly yielding reasonable yellow emission. The overall white light emission properties are enhanced, achieving CIE coordinates (0.36, 0.39) and color temperature (4643 K) similar to daylight. Employing intermolecular exciplex emission in OLEDs simplifies the device architecture via its dual functionality as a host and as an emitter.Graphical abstract

A Zn(II) metal−organic framework with organic fluorescent ligands and hydrogen-bonding network for effectively sensing Al3+ and Ga3+ ions, and proton conduction

Energy shortage and environmental pollution become increasingly serious. Thus, there is urgent need to develop new functional materials to deal with these problems. Metal−organic frameworks (MOFs) are ideal candidates for fluorescence sensing pollutants and proton conduction. A benzothiadiazole-based three-dimensional (3D) Zn(II) MOF with the formula of {[(CH3)2NH2][Zn3(bbip)(BTDI)1.5(OH)]·DMF·MeOH·3H2O}n (JXUST-13, bbip = 2,6-bis(benzimidazol-1-yl)pyridine and H4BTDI = 5,5′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diisophthalic acid) with fluorescent ligands and rich hydrogen bond framework was used as a cation fluorescence sensor and proton conduction material. The fluorescence experiment revealed that JXUST-13 could detect Al3+ and Ga3+ ions by fluorescence blue shift and slight fluorescence enhancement. And it showed high sensitivity, good selectivity, anti-interference performance and cyclicity. The detection limits of JXUST-13 toward Al3+ and Ga3+ ions were 4.0 μM and 0.67 μM, respectively. Importantly, it could be rapidly detected by fluorescent test strips and naked eyes. The sensing mechanism may be due to the presence of electron transfer and the formation of exciplex. Proton conduction result indicated that the maximum conductivity value of JXUST-13 was 1.97 × 10−5 S·cm−1 at 80 °C and 98% RH. And the conductivity increased with humidity and temperature. The activation energy (Ea) value of JXUST-13 was 0.47 eV, which revealed the Vehicle mechanism. Therefore, JXUST-13 could be considered as a rare difunctional materials of blue-shifted fluorescence sensor for Al3+, Ga3+ ions and proton conduction.

Experimental and theoretical studies on charge transfer complex formed by TCTA and TPBi

The studies on charge transfer (CT) complex formed by 4,4,4″-tris(N-carbazolyl)-triphenylamine (TCTA) and 1,3,5-tris(N-phenylbenzimidazol-2-yl) benzene (TPBi) were carried out by experiment and simulation calculations. Experimentally, exciplex-forming in TCTA:TPBi mixture is observed and electroplex is formed for TCTA/TPBi bi-layer structure. The density functional theory via DMol3 package was performed to explore the geometrical structures, stability, and electronic structures of the complexes. The calculation results demonstrate that geometrically stable structure of the complex is assumed to enable electroplex-forming because the molecular planes of donor and acceptor are separated by 5.5 Å. However, the formation of exciplex requires a small intermolecular separation of below 4 Å, which is relatively unstable for TCTA−TPBi complex and has to be driven by an external force. The requisition can be fulfilled in TCTA:TPBi mixture due to a reduction of intermolecular interval caused by tight molecular packing and strong intermolecular interaction deriving from mixing. The emission of exciplex species is thereof observed in TCTA:TPBi mixture and analogue electroplex in TCTA/TPBi bi-layer system. The calculated frontier molecular orbitals of the complexes exhibit the lowest unoccupied molecular orbital (LUMO) is positioned on TPBi and the highest occupied molecular orbital (HOMO) on TCTA, inferring that the emission of the CT complexes is originated from electron cross transition between the LUMO of TPBi and HOMO of TCTA. Meanwhile, the greater overlap of the molecular orbitals and larger oscillator strength of lowest-lying singlet excited states manifest that the CT complex in TCTA:TPBi mixture can be more efficiently produced, resulting in better electroluminescent performance, compared to TCTA/TPBi system.

Exciplex Emission and Förster Resonance Energy Transfer in Polycyclic Aromatic Hydrocarbon-Based Bischromophoric Cyclophanes and Homo[2]catenanes.

Energy transfer and exciplex emission are not only crucial photophysical processes in many living organisms but also important for the development of smart photonic materials. We report, herein, the rationally designed synthesis and characterization of two highly charged bischromophoric homo[2]catenanes and one cyclophane incorporating a combination of polycyclic aromatic hydrocarbons, i.e., anthracene, pyrene, and perylene, which are intrinsically capable of supporting energy transfer and exciplex formation. The possible coconformations of the homo[2]catenanes, on account of their dynamic behavior, have been probed by Density Functional Theory calculations. The unique photophysical properties of these exotic molecules have been explored by steady-state and time-resolved absorption and fluorescence spectroscopies. The tetracationic pyrene-perylene cyclophane system exhibits emission emanating from a highly efficient Förster resonance energy transfer (FRET) mechanism which occurs in 48 ps, while the octacationic homo[2]catenane displays a weak exciplex photoluminescence following extremely fast (<0.3 ps) exciplex formation. The in-depth fundamental understanding of these photophysical processes involved in the fluorescence of bischromophoric cyclophanes and homo[2]catenanes paves the way for their use in future bioapplications and photonic devices.

Key Determining Factors for the Emitting Dipole Orientation of Exciplexes

AbstractExciplexes have attracted interest as hosts and emitters that provide high efficiency and long lifetimes in organic light‐emitting diodes (OLEDs). However, the emitting dipole orientation (EDO) of exciplexes has been overlooked despite its importance for high efficiency. In this work, the EDO of exciplexes is investigated by changing the p‐type host. Various p‐type hosts are mixed with 2,4,6‐tris[3‐(diphenylphosphinyl)phenyl]‐1,3,5‐triazine for exciplex formation. The EDO of the exciplexes is aligned vertically with p‐type hosts having hydrophobic or electron‐poor central units while dispersing the highest occupied molecular orbitals (HOMOs) at the end of the molecules, whereas it is isotropic with p‐type hosts having widely distributed HOMO on the whole molecular structure without any orientation‐managing central unit. The results show that EDO can be correlated with the outcoupling efficiency of exciplex OLEDs.