Huifang Shi

Conjugated Asymmetric Donor‐Substituted 1,3,5‐Triazines: New Host Materials for Blue Phosphorescent Organic Light‐Emitting Diodes

Conjugated asymmetric donor-substituted 1,3,5-triazines (ADTs) have been synthesized by nucleophilic substitution of organolithium catalyzed by [Pd(PPh(3))(4)]. Theoretical and experimental investigations show that ADTs possess high solubility and thermostability, high fluorescent quantum yield (35%), low HOMO (-6.0 eV) and LUMO (-2.8 eV), and high triplet energy (E(T), 3.0 eV) according to the different substitution pattern of triazine. The application as host materials for blue PHOLEDs yielded a maximum current efficiency of 20.9 cd A(-1), a maximum external quantum efficiency of 9.8%, and a brightness of 9671 cd m(-2) at 5.4 V, making ADTs good candidates for optoelectronic devices.

Exceptional Blueshifted and Enhanced Aggregation‐Induced Emission of Conjugated Asymmetric Triazines and Their Applications in Superamplified Detection of Explosives

A novel conjugated asymmetric donor-acceptor (CADA) strategy for preventing the redshift in photoluminescence, as well as preserving the merits of donor-acceptor architectures, was proposed and demonstrated for two triazine derivatives, which showed highly efficient, narrow, and blueshifted ultraviolet light emission in solid films along with special aggregation-induced emission behavior. A mechanism of aggregation-induced locally excited-state emission by suppressing the twisted intramolecular charge-transfer emission for the spectacular optoelectronic phenomena of these CADA molecules was suggested on the basis of both experimental measurements and theoretical calculations. By taking advantage of this special CADA architecture, fluorescent probes based on aggregates of conjugated asymmetric triazines in THF/water for the detection of explosives show superamplified detection of picric acid with high quenching constants (>1.0 × 10(7) M(-1)) and a low detection limit of 15 ppb.

In situ photoluminescence investigation of doped Alq

We report the photoluminescence (PL) properties measured in situ from vacuum-deposited organic films of tris-(8-hydroxyquinoline) aluminum (Alq) doped with 4-(dicyanomethylene)-2-methyl-6(p-dimethylaminostyryl)-4H-pyran (DCM), where the red emission from the guest molecules is due to Forster energy transfer of excited state energy from host to guest. Both bare DCM-doped Alq (Alq:DCM) and bilayer Alq/Alq:DCM films have been studied, with the thickness of the Alq overlayer continuously varied in the latter case. The PL spectra from the bilayer structure contain no Alq contribution when its thickness is below 2.4 nm. Taking the value as the maximum distance for which the Alq exciton can travel in the film and still transfer its energy to a DCM molecule, the minimum DCM concentration in Alq:DCM necessary to produce red emission only can be estimated at 0.31 wt %. The most efficient red emission appears at the DCM concentration of about 1.7 wt %, at which more than 90% Alq-originated excitons are involved in t...

Hyper-Branched Phosphorescent Conjugated Polyelectrolytes for Time-Resolved Heparin Sensing

A series of hyper-branched cationic conjugated polyelectrolytes containing different contents of phosphorescent Ir(III) complex has been designed and synthesized successfully. Their photophysical properties in both aqueous solution and solid film are investigated and their morphologies in aqueous solution are observed by TEM. Nanoparticles with the size of 80-100 nm have been formed in aqueous solution through the self-assembly of polymers. An energy transfer process from host polyfluorene to guest Ir(III) complex exists and becomes more efficient in the solid films. Importantly, this series of hyper-branched polymers can be applied as light-up heparin probes with good selectivity, high sensitivity, and naked-eye detection through electrostatic interaction between polymers and heparin. Quantification for heparin in aqueous solution can be realized in the range of 0-44 μM in the buffer solution. Detection limit can reach as low as 50 nM. More meaningfully, time-resolved photoluminescence technique is utilized successfully in the heparin sensing to eliminate the background fluorescence interference effectively and enhance the sensing sensitivity in the complicated media.

Visible-Light-Excited Ultralong Organic Phosphorescence by Manipulating Intermolecular Interactions

Visible light is much more available and less harmful than ultraviolet light, but ultralong organic phosphorescence (UOP) with visible-light excitation remains a formidable challenge. Here, a concise chemical approach is provided to obtain bright UOP by tuning the molecular packing in the solid state under irradiation of available visible light, e.g., a cell phone flashlight under ambient conditions (room temperature and in air). The excitation spectra exhibit an obvious redshift via the incorporation of halogen atoms to tune intermolecular interactions. UOP is achieved through H-aggregation to stabilize the excited triplet state, with a high phosphorescence efficiency of 8.3% and a considerably long lifetime of 0.84 s. Within a brightness of 0.32 mcd m-2 that can be recognized by the naked eye, UOP can last for 104 s in total. Given these features, ultralong organic phosphorescent materials are used to successfully realize dual data encryption and decryption. Moreover, well-dispersed UOP nanoparticles are prepared by polymer-matrix encapsulation in an aqueous solution, and their applications in bioimaging are tentatively being studied. This result will pave the way toward expanding metal-free organic phosphorescent materials and their applications.

Imaging-Guided Drug Release from Glutathione-Responsive Supramolecular Porphysome Nanovesicles

Drug delivery systems that can be employed to load anticancer drugs and release them triggered by a specific stimulus, such as glutathione, are of great importance in cancer therapy. In this study, supramolecular porphysome nanovesicles that were self-assembled by amphiphilic porphyrin derivatives were successfully constructed, mainly driven by the π-π stacking, hydrogen bonding, and hydrophobic interactions, and were used as carriers of anticancer drugs. The nanovesicles are monodispersed in shape and uniform in size. The drug loading and in vitro drug release investigations indicate that these nanovesicles are able to encapsulate doxorubicin (DOX) to achieve DOX-loaded nanovesicles, and the nanovesicles could particularly release the loaded drug triggered by a high concentration of glutathione (GSH). More importantly, the drug release in cancer cells could be monitored by fluorescent recovery of the porphyrin derivative. Cytotoxicity experiments show that the DOX-loaded nanovesicles possess comparable therapeutic effect to cancer cells as free DOX. This study presents a new strategy in the fabrication of versatile anticancer drug nanocarriers with stimuli-responsive properties. Thus, the porphysome nanovesicles demonstrated here might offer an opportunity to bridge the gap between intelligent drug delivery systems and imaging-guided drug release.

A ratiometric probe composed of an anionic conjugated polyelectrolyte and a cationic phosphorescent iridium(III) complex for time-resolved detection of Hg(II) in aqueous media.

A hybrid complex composed of an anionic conjugated polyelectrolyte (PFB-SO3Na) and a cationic phosphorescent Ir(III) oligomer is formed through electrostatic interaction by simple physical mixing in aqueous media. Due to their opposite charges and their effective spectral overlap, fluorescence resonance energy transfer occurs from the blue-emissive PFB-SO3Na to the red-emissive phosphorescent Ir(III) complex, which allows ratiometric and colorimetric Hg(2+) sensing in aqueous solution with good selectivity, sensitivity, as well as visible detection. Time-resolved photoluminescence is applied for Hg(2+) detection, which can effectively eliminate the background interference and improve the sensing sensitivity and signal-to-noise ratio in complicated media.

Relationships between main-chain chirality and photophysical properties in chiral conjugated polymers

A series of R- and S-binaphthyl-containing polyfluorenes, bearing different contents and types of axial chirality in the main chain, have been synthesized through Suzuki polycondensation to investigate the influence of the covalently incorporated chirality on the photophysical properties of chiral conjugated polymers. The experimental measurements obtained by UV-Vis and photoluminescence (PL) spectroscopy, cyclic voltammetry, and circular dichroism spectroscopy reveal that the chiral copolymers possess high thermostability, high luminescence efficiency, reversible electrochemical properties, and intrachain transferred dichroism. Surprisingly, the R-chiral polymers exhibit better spectral thermostability, stronger suppressing ability upon the β-phase formation of the main-chain, and higher PL quantum efficiency than S-chiral polymers in solid films. The theoretical insights obtained by either ab initio density functional theory (DFT) calculations or molecular dynamics (MD) simulations suggest that these differences probably resulted from the more planar chain conformation of S-chiral polymers, which leads to stronger interchain interaction and an increased tendency to form inefficient and unstable excimers or quenchers. The different effects of enantiomers on the photophysical properties of chiral conjugated polymers may provide an import update in the understanding of chiro-optics.

Modulation of singlet and triplet excited states through σ spacers in ternary 1,3,5-triazines

A series of ternary asymmetric triazines with tunable singlet and triplet excited states were successfully synthesized on the basis of σ-spacer methodology and a facile synthetic route. The optoelectronic properties are dominated by the conjugated donor–acceptor (D–A) backbone of peripheral carbazoles (D) and triazine core (A), and can be further modulated via the partially interrupted conjugation between the core and the third substituents by the σ spacers of N–CH3, NH, O, S and OSO, which offers new opportunities to fine tune the electronic structures and properties of triazines.

Insight into Chirality on Molecular Stacking for Tunable Ultralong Organic Phosphorescence

A new levorotatory compound ((S)-9,9′-(6-(1-phenylethoxy)-1,3,5-triazine-2,4-diyl)bis(9H-carbazole)) and its corresponding racemic compound show different intermolecular interactions to restrain nonradiative transition, resulting in an enhanced ultralong organic phosphorescence lifetime from 229.0 ms to 419.8 ms. This work will provide a new insight into the chirality of organic molecules to adjust the ultralong phosphorescence.