Thermochromic aggregation-induced dual phosphorescence via temperature-dependent sp3-linked donor-acceptor electronic coupling.
ABSTRACT: Aggregation-induced emission (AIE) has proven to be a viable strategy to achieve highly efficient room temperature phosphorescence (RTP) in bulk by restricting molecular motions. Here, we show that by utilizing triphenylamine (TPA) as an electronic donor that connects to an acceptor via an sp3 linker, six TPA-based AIE-active RTP luminophores were obtained. Distinct dual phosphorescence bands emitting from largely localized donor and acceptor triplet emitting states could be recorded at lowered temperatures; at room temperature, only a merged RTP band is present. Theoretical investigations reveal that the two temperature-dependent phosphorescence bands both originate from local/global minima from the lowest triplet excited state (T1). The reported molecular construct serves as an intermediary case between a fully conjugated donor-acceptor system and a donor/acceptor binary mix, which may provide important clues on the design and control of high-freedom molecular systems with complex excited-state dynamics.
Project description:Carbon dots (CDs) with red-emitting room-temperature phosphorescence (RTP) are rarely reported because of the increasing nonradiative decay of the excited states and the decreasing energy gap between the excited states and ground states. Herein, we demonstrate a facile strategy for modulating the RTP properties of CDs in terms of donor-acceptor energy transfer (EnT) in the CDs-in-zeolite system. Upon tuning of the heteroatoms (Zn2+, Mn2+) doped in the aluminophosphate zeolite frameworks, CDs@zeolite composites with green and red phosphorescence have been prepared via in situ hydrothermal synthesis. In such composites, the zeolite matrix provides an efficient confinement role in stabilizing the triplet states of CDs. Significantly, the Mn-doped zeolite could act as an energy acceptor allowing EnT from excitons of CDs to the dopant in the host matrix, generating the intriguing red RTP behavior. This work provides an effective strategy for developing CD-based composite materials with special RTP emissions as well as new fields for applications.
Project description:Understanding the excited-state dynamics and conformational relaxation in thermally activated delayed fluorescence (TADF) molecules, including conformations that potentially support intramolecular through-space charge transfer, can open new avenues for TADF molecular design as well as elucidate complex photophysical pathways in structurally complex molecules. Emissive molecules comprising a donor (triphenylamine, TPA) and an acceptor (triphenyltriazine, TRZ) bridged by a second donor (9,9-dimethyl-9-10-dihydroacridin, DMAC, or phenoxazine, PXZ) are synthesized and characterized. In solution, the flexibility of the sp3-hybridized carbon atom in DMAC of DMAC-TPA-TRZ, compared to the rigid PXZ, allows significant conformational reorganization, giving rise to multiple charge-transfer excited states. As a result of such a reorganization, the TRZ and TPA moieties become cofacially aligned, driven by a strong dipole-dipole attraction between the TPA and TRZ units, forming a weakly charge-transfer dimer state, in stark contrast to the case of PXZ-TPA-TRZ where the rigid PXZ bridge only supports a single PXZ-TRZ charge transfer (CT) state. The low-energy TPA-TRZ dimer is found to have a high-energy dimer local triplet state, which quenches delayed emission because the resultant singlet CT local triplet energy gap is too large to mediate efficient reverse intersystem crossing. However, organic light-emitting diodes using PXZ-TPA-TRZ as an emitting dopant resulted in external quantum efficiency as high as 22%, more than two times higher than that of DMAC-TPA-TRZ-based device, showing the impact that such intramolecular reorganization and donor-acceptor dimerization have on TADF performance.
Project description:Conjugated molecular crystals with persistent room-temperature phosphorescence (RTP) are promising materials for sensing, security, and bioimaging applications. However, the electronic structures that lead to efficient persistent RTP are still unclear. Here, the electronic structures of tetraphenylmethane (C(C6H5)4), tetraphenylsilane (Si(C6H5)4), and tetraphenylgermane (Ge(C6H5)4) showing blue-green persistent RTP under ambient conditions are investigated. The persistent RTP of the crystals originates from minimization of triplet exciton quenching at room temperature not suppression of molecular vibrations. Localization of the highest occupied molecular orbitals (HOMOs) of the steric and highly symmetric conjugated crystal structures decreases the overlap of intermolecular HOMOs, minimizing triplet exciton migration, which accelerates defect quenching of triplet excitons. The localization of the HOMOs over the highly symmetric conjugated structures also induces moderate charge-transfer characteristics between high-order singlet excited states (S m ) and the ground state (S0). The combination of the moderate charge-transfer characteristics of the S m -S0 transition and local-excited state characteristics between the lowest excited triplet state and S0 accelerates the phosphorescence rate independent of the vibration-based nonradiative decay rate from the triplet state at room temperature. Thus, the decrease of triplet quenching and increase of phosphorescence rate caused by the HOMO localization contribute to the efficient persistent RTP of Ge(C6H5)4 crystals.
Project description:The correlation between molecular packing structure and its room-temperature phosphorescence (RTP), hence rational promotion of the intensity, remains unclear. We herein present racemism enhanced RTP chiral chromophores by 2,2-bis-(diphenylphosphino)-1,1-napthalene (rac-BINAP) in comparison to its chiral counterparts. The result shows that rac-BINAP in crystal with denser density, consistent with a long standing Wallach's rule, exhibits deeper red RTP at 680?nm than that of the chiral counterparts. The cross packing between alternative R- and S- forms in rac-BINAP crystal significantly retards the bimolecular quenching pathway, triplet-triplet annihilation (TTA), and hence suppresses the non-radiative pathway, boosting the RTP intensity. The result extends the Wallach's rule to the fundamental difference in chiral-photophysics. In electroluminescence, rac-BINAP exhibits more balanced fluorescence versus phosphorescence intensity by comparison with that of photoluminescence, rendering a white-light emission. The result paves an avenue en route for white-light organic light emitting diodes via full exploitation of intrinsic fluorescence and phosphorescence.
Project description:Throwing light upon the structure-property relationship of the excited state properties for next-generation fluorescent materials is crucial for the organic light emitting diode (OLED) field. Herein, we designed and synthesized three donor-acceptor (D-A) structure compounds based on a strong spin orbit coupling (SOC) acceptor benzo[a, c]phenazine (DPPZ) to research on the three typical types of excited states, namely, the locally-excited (LE) dominated excited state (CZP-DPPZ), the hybridized local and charge-transfer (HLCT) state (TPA-DPPZ), and the charge-transfer (CT) dominated state with TADF characteristics (PXZ-DPPZ). A theoretical combined experimental research was adopted for the excited state properties and their regulation methods of the three compounds. Benefiting from the HLCT character, TPA-DPPZ achieves the best non-doped device performance with maximum brightness of 61,951 cd m<sup>-2</sup> and maximum external quantum efficiency of 3.42%, with both high photoluminescence quantum efficiency of 40.2% and high exciton utilization of 42.8%. Additionally, for the doped OLED, PXZ-DPPZ can achieve a max EQE of 9.35%, due to a suppressed triplet quenching and an enhanced SOC.
Project description:Due to inefficient molecular design strategies, two-photon-excited ultralong organic room temperature phosphorescence (TPUOP) has not yet been reported in single-component materials. Herein, we present an innovative design method by dual-channel triplet harvesting to obtain the first bright TPUOP molecule with a lifetime of 0.84 s and a quantum efficiency of 16.6%. In compound o-Cz the donor and acceptor units are connected at the ortho position of benzophenone, showing intramolecular space charge transfer. Therefore, the two-photon absorption ability is improved due to the enhanced charge transfer character. Moreover, the small energy gap boosts dual-channel triplet harvesting via ultralong thermally activated delayed fluorescence and H-aggregation phosphorescence, which suppresses the long-lived triplet concentration quenching. Through two-photon absorption, a near-infrared laser (808 nm) is able to trigger the obvious ultralong emission under ambient conditions. This research work provides valuable guidance for designing near-infrared-excited ultralong organic room temperature phosphorescence materials.
Project description:Achieving highly efficient phosphorescence in purely organic luminophors at room temperature remains a major challenge due to slow intersystem crossing (ISC) rates in combination with effective non-radiative processes in those systems. Most room temperature phosphorescent (RTP) organic materials have O- or N-lone pairs leading to low lying (n, ?*) and (?, ?*) excited states which accelerate kisc through El-Sayed's rule. Herein, we report the first persistent RTP with lifetimes up to 0.5?s from simple triarylboranes which have no lone pairs. RTP is only observed in the crystalline state and in highly doped PMMA films which are indicative of aggregation induced emission (AIE). Detailed crystal structure analysis suggested that intermolecular interactions are important for efficient RTP. Furthermore, photophysical studies of the isolated molecules in a frozen glass, in combination with DFT/MRCI calculations, show that (?, B p)?(?, B p) transitions accelerate the ISC process. This work provides a new approach for the design of RTP materials without (n, ?*) transitions.
Project description:A novel bistable molecular shuttle, composed of a Pt(ii) porphyrin-containing dibenzocrown-8 macrocycle threaded onto two different recognition sites (secondary dialkylammonium (NH2+) and 4,4'-bipyridinium (Bpym2+) units), and the anthracene (Anth) moiety as one terminal stopper, was synthesized by click chemistry. Its acid-base switchable shuttling could be addressed by both the room temperature phosphorescence (RTP) emission signals of the Pt(ii) porphyrin moiety and the fluorescence emission of the Anth unit, as well as their lifetime changes. When the macrocycle was switched to be located on the NH2+ site close to Anth, the Pt(ii) porphyrin moiety exhibited strong RTP emission, excited in the Anth band at 370 nm. This was due to the distance-dependent efficient singlet energy transfer between the Anth unit and the porphyrin moiety, followed by intersystem crossing from a singlet to a triplet state in Pt(ii) porphyrin, while its RTP emission dramatically decreased when located on the Bpym2+ site far from the Anth unit. When excited in the porphyrin band at 402 nm, the RTP emission lifetimes changed obviously. This is the first rotaxane-type molecular shuttle whose shuttling has been encoded by RTP signals.
Project description:Knowing the underlying photophysics of thermally activated delayed fluorescence (TADF) allows proper design of high efficiency organic light-emitting diodes. We have proposed a model to describe reverse intersystem crossing (rISC) in donor-acceptor charge transfer molecules, where spin-orbit coupling between singlet and triplet states is mediated by one of the local triplet states of the donor (or acceptor). This second order, vibronically coupled mechanism describes the basic photophysics of TADF. Through a series of measurements, whereby the energy ordering of the charge transfer (CT) excited states and the local triplet are tuned in and out of resonance, we show that TADF reaches a maximum at the resonance point, substantiating our model of rISC. Moreover, using photoinduced absorption, we show how the populations of both singlet and triplet CT states and the local triplet state change in and out of resonance. Our vibronic coupling rISC model is used to predict this behaviour and describes how rISC and TADF are affected by external perturbation.
Project description:The influence of non-covalent ?-? orbital interactions on triplet-triplet energy transfer (TTET) through tuning of the donor excitation energy remains basically unexplored. In the present work, we have investigated intermolecular TTET using donor moieties covalently linked to a rigid cholesterol (Ch) scaffold. For this purpose, diaryl ketones of ?,?* electronic configuration tethered to ?- or ?-Ch were prepared from tiaprofenic acid (TPA) and suprofen (SUP). The obtained systems TPA-?-Ch, TPA-?-Ch, SUP-?-Ch and SUP-?-Ch were submitted to photophysical studies (laser flash photolysis and phosphorescence), in order to delineate the influence of steric shielding and ?-? orbital interactions on the rate of TTET to a series of energy acceptors. As a matter of fact, fine tuning of the donor triplet energy significantly modifies the rate constants of TTET in the absence of diffusion control. The experimental results are rationalized by means of theoretical calculations using first principles methods based on DFT as well as molecular dynamics.