Efficient near-infrared emission benefits from slowing down the internal conversion process.

Organic deep-red (DR) and near-infrared (NIR) emitters with high photoluminescence quantum yield (PLQY) are rare due to the strong non-radiative (knr) decay. Here, we report two DR/NIR emitters with high PLQY, TPANZPyPI and TPANZ3PI. Interestingly, the TPANZPyPI film exhibits 46.5% PLQY at 699 nm. Theoretical calculations indicate that TPANZPyPI can achieve this high PLQY in the near-infrared emission region due to its small S1 to S0 internal conversion (IC) rate. Meanwhile, research has found that, compared to TPANZ3PI, TPANZPyPI with a more rigid structure can effectively suppress the T2 to T1 IC process, which is conducive to higher exciton utilization efficiency (EUE). TPANZPyPI's non-doped OLED shows NIR emission with 4.6% @ 684 nm maximum external quantum efficiency (EQEmax). Its doped OLEDs radiate DR with an EQEmax of 6.9% @ 666 nm. These EQEs are among the highest values for hybridized local charge transfer state materials emitting more than 640 nm. This work demonstrates for the first time, based on a combination of theory and experiment, that increasing the molecular rigidity can inhibit the excited state IC process in addition to the S1 to S0 IC, realizing efficient electroluminescence.

Transforming Thermally Activated Delayed Fluorescence to Room-Temperature Phosphorescence through Modulation of the Donor in Charge-Transfer Cocrystals.

A cocrystallization strategy is used through incorporation of 1,2,4,5-tetracyanobenzene (TCNB) as an acceptor with halogen-substituent thioxanthone (TX) derivatives as donors. The resulting cocrystals TT-R (R = H, F, Cl, Br, or I) transform the thermally activated delayed fluorescence emission in the TT-H, TT-F, and TT-Cl cocrystals to room-temperature phosphorescence in the TT-Br and TT-I cocrystals. Definite crystal packing structures demonstrate a 1:1 alternative donor-acceptor stacking in the TT-H cocrystal, a 2:1 alternative donor-acceptor stacking in the TT-F and TT-Cl cocrystals, and a separate stacking of donor and acceptor in the TT-Br and TT-I cocrystals. A transformation law can be revealed that with an increase in atomic number from H, F, Cl, Br, to I, the cocrystals show the structural transformation of the number of aggregated TX-R molecules from monomers to dimers and finally to multimers. This work will facilitate an understanding of the effect of halogen substituents on the crystal packing structure and luminescence properties in the cocrystals.

Photo-Responsive Dynamic Organic Room-Temperature Phosphorescence Materials Based on a Functional Unit Combination Strategy.

A rational molecular design strategy facilitates the development of a purely organic room-temperature phosphorescence (RTP) material system with precisely regulated luminescence properties, which surely promotes its functional integration and intelligent application. Here, a functional unit combination strategy is proposed to design novel RTP molecules combining a folding unit with diverse luminescent cores. The different luminescent cores are mainly responsible for tunable RTP properties, while the folding unit contributes to the spin-orbit coupling (SOC) enhancement, which makes the RTP material design as workable as the building block principle. By this strategy, a series of color/lifetime-tunable RTP materials is achieved with unique photo-responsive RTP enhancement when subjected to UV irradiation, which expands their application scenarios in reusable privacy tags, advanced "4D" encryption, and phase separation analysis of blended polymers. This work suggests a simple and effective strategy to design purely organic RTP materials with tunable color and lifetime, and also provides new application options for photo-responsive dynamic RTP materials.

A functional unit combination strategy for enhancing red room-temperature phosphorescence.

Red room-temperature phosphorescence (RTP) materials based on non-metallic organic compounds are less reported compared to the commonly found green RTP materials. Here, we propose a novel approach to obtain red RTP materials by integrating and combining two functional units, resembling a jigsaw puzzle. In this approach, benzo[c][2,1,3]thiadiazole (BZT) serves as the red RTP unit, while a folding unit containing sulphur/oxygen is responsible for enhancing spin-orbit coupling (SOC) to accelerate the intersystem crossing (ISC) process. Three new molecules (SS-BZT, SO-BZT, and OO-BZT) were designed and synthesized, among which SS-BZT and SO-BZT with folded geometries demonstrate enhanced red RTP in their monodisperse films compared to the parent BZT. Meanwhile, the SS-BZT film shows a dual emission consisting of blue fluorescence and red RTP, with a significant spectral separation of approximately 150 nm, which makes the SS-BZT film highly suitable for applications in optical oxygen sensing and ratiometric detection. Within the oxygen concentration range of 0-1.31%, the SS-BZT film demonstrates a quenching constant of 2.66 kPa-1 and a quenching efficiency of 94.24%, indicating that this probe has the potential to accurately detect oxygen in a hypoxic environment.

A Heavy-atom-free Molecular Motif Based on Symmetric Bird-like Structured Tetraphenylenes with Room-Temperature Phosphorescence (RTP) Afterglow over 8 s.

In recent years, pure organic room-temperature phosphorescence (RTP) with highly efficient and long-persistent afterglow has drawn substantial awareness. Commonly, spin-orbit coupling can be improved by introducing heavy atoms into pure-organic molecules. However, this strategy will simultaneously increase the radiative and non-radiative transition rate, further resulting in dramatic decreases in the excited state lifetime and afterglow duration. Here in this work, a highly symmetric bird-like structure tetraphenylene (TeP), and its three symmetrical halogenated derivatives (TeP-F, TeP-Cl and TeP-Br) are synthesized, while their RTP properties and mechanisms are systematically investigated by both theoretical and experimental approaches. As the results, the rigid, highly twisted conformation of TeP restricts the non-radiative processes of RTP and gives rise to the enhancement of electron-exchange, which can contribute to the RTP radiation process. Despite the faint RTP of the bromine and chlorine-substituted ones (TeP-Br, TeP-Cl), the fluoro-substituted TeP-F exhibited a long phosphorescent lifetime up to 890 ms, corresponding to an extremely long RTP afterglow over 8 s, which could be incorporated into the best series of non-heavy-atom RTP materials reported in previous literature.

Pressure-induced room-temperature phosphorescence enhancement based on purely organic molecules with a folded geometry.

The pressure-dependent luminescence behavior of purely organic compounds is an important topic in the field of stimulus-responsive smart materials. However, the relevant studies are mainly limited to the investigation of fluorescence properties, while room-temperature phosphorescence (RTP) of purely organic compounds has not been investigated. Here, we filled in this gap regarding pressure-dependent RTP by using a model molecule selenanthrene (SeAN) with a folded geometry. For the first time to the best of our knowledge, a unique phenomenon involving pressure-induced RTP enhancement was discovered in an SeAN crystal, and an underlying mechanism involving folding-induced spin-orbit coupling enhancement was revealed. Pressure-induced RTP enhancement was also observed in an analog of SeAN also showing a folded geometry, but in this case yielded a white-light emission that is very rare in purely organic RTP-displaying materials.

Robust formation of discrete non-covalent pyrene dimers in an amorphous film by strong π-π interaction.

A pyrene-based non-covalent dimer in a crystal showed a strengthened π-π interaction, which was robust enough against external disturbances. Such a strong π-π interaction made the pyrene-based dimer easily form in the amorphous film, indicating that the dimer could potentially work as the monomer.

Confined-domain crosslink-enhanced emission effect in carbonized polymer dots.

Revealing the photoluminescence (PL) origin and mechanism is a most vital but challenging topic of carbon dots. Herein, confined-domain crosslink-enhanced emission (CEE) effect was first studied by a well-designed model system of carbonized polymer dots (CPDs), serving as an important supplement to CEE in the aspect of spatial interactions. The "addition-condensation polymerization" strategy was adopted to construct CPDs with substituents exerting different degrees of steric hindrance. The effect of confined-domain CEE on the structure and luminescence properties of CPDs have been systematically investigated by combining characterizations and theoretical calculations. Such tunable spatial interactions dominated the coupling strength of the luminophores in one particle, and eventually resulted in the modulated PL properties of CPDs. These findings provide insights into the structural advantages and the PL mechanism of CPDs, which are of general significance to the further development of CPDs with tailored properties.

Folding-Induced Spin-Orbit Coupling Enhancement for Efficient Pure Organic Room-Temperature Phosphorescence.

For the direct luminescence of triplet excitons, different mechanisms have been proposed for realizing pure organic room-temperature phosphorescence (RTP). To further verify the mechanism of folding-induced spin-orbit coupling (SOC) enhancement, two analogues of thianthrene (TA) were introduced by gradually replacing the sulfur atom with an oxygen atom for a systematical comparison, corresponding to phenoxathiine (PX) and dioxins (DX) molecules with increasing folding dihedral angles (or decreasing degrees of folding). Photophysical measurements show an obviously enhanced RTP efficiency from DX and PX to TA, which is consistent with their greatly enhanced SOC with a decrease in folding dihedral angle. The folding angle-dependent SOC calculations for each molecule reveal that this enhanced RTP is dominated by folding-induced SOC enhancement, in contrast with the negligible heavy-atom effect from oxygen to sulfur. This work further validates the rationality of the folding-induced SOC enhancement mechanism, which provides an innovative molecular design strategy for developing efficient pure organic RTP materials using folding structures.

Pressure-Induced Local Excitation Promotion: New Route toward High-Efficiency Aggregate Emission Based on Multimer Excited State Modulation.

Achieving high-efficiency solid state emission is essential for practical applications of organic luminescent materials. However, intermolecular interactions generally induce formation of multimeric aggregate excited states with deficient emissive ability, making it extremely challenging to enhance emission in aggregated states. Here we demonstrate a novel strategy of continuously regulating multimeric excitation constituents with a high-pressure technique successfully enhancing the emission in a representative organic charge-transfer material, Laurdan (6-lauroyl-N,N-dimethyl-2-naphthylamine). The Laurdan crystal exhibits distinct emission enhancement up to 4.1 GPa accompanied by a shift in the emission color from blue to cyan. Under compression, the π-π interplanar distance in Laurdan multimers is reduced, and intermolecular wave function diffusion is demonstrated to be improved simultaneously, which results in local excitation promotion and thus enhanced emission. Our findings not only provide new insights into multimeric excited state emission modulation but also pave the way for the further design of high-performance aggregated luminophores.

Multicolour Fluorescence Based on Excitation-Dependent Electron Transfer Processes in o-Carborane Dyads.

Organic materials with excitation wavelength-dependent (Ex-de) emission are highly attractive for anticounterfeiting, optoelectronics and bioassay applications; however, the realization of Ex-de fluorescence, independent of aggregation states, remains a challenge. We herein report a photoinduced electron transfer (PeT) strategy to design Ex-de fluorescence materials by manipulating the relaxation pathways of multiple excited states. As expected, the o-carborane dyad presents a clear Ex-de fluorescence colour in the aggregated states, resulting from the tunable relative intensity of the dual-fluorescence spectra. Taking TP[1]B as an example, the amorphous powders emitted bright blue-violet, white and yellow colours under 390 nm, 365 nm and 254 nm UV illumination, respectively. Importantly, multicolour, flexible and transparent films as well as an anticounterfeiting application using this o-carborane dyad are demonstrated.

Construction of Proton Transport Highways Induced by Polarity-Driving in Proton Exchange Membranes to Enhance the Performance of Fuel Cells.

The approach to constructing proton transport channels via direct adjustments, including hydrophilia and analytical acid concentration in hydrophilic domains, has been proved to be circumscribed when encouraging the flatter hydrophilic-hydrophobic microphase separation structures and reducing conductivity activation energy. Here, we propose a constructive solution by regulating the polarity of hydrophobic domains, which indirectly varies the aggregation and connection of hydrophilic ion clusters during membrane formation, enabling orderly self-assembly and homogeneously distributed microphase structures. Accordingly, a series of comb-shaped polymers were synthesized with diversified optimization, and more uniformly distributed ion cluster lattices were subsequently observed using high-resolution transmission electron microscopy. Simultaneously, combining with density functional theory calculations, we analyzed the mechanism of membrane degradations caused by hydroxyl radical attacks. Experimental results demonstrated that, facilitated by proper molecule polarity, beneficial changes of bond dissociation energy could extend the membrane lifetime more than the protection from side chains near ether bonds, which were deemed to reduce the probability of attacks by the steric effect. With the optimal strategy chosen among various trials, the maximum power density of direct methanol fuel cell and H2/air proton exchange membrane fuel cell was enhanced to 95 and 485 mW cm-2, respectively.

Tuning Organic Microcrystal Morphologies through Crystal Engineering Strategies toward Anisotropic Optical Waveguide.

The construction of organic optoelectronic materials with desirable size and morphology remains a challenge now. Crystal engineering strategies (polymorphs and cocrystals) provide convenience for tailoring molecular packing and further controlling the growth morphology and photofunctionality of materials. Herein, we prepare polymorphic 2D plate crystals and 3D microhelixes by assembly of a cyanostilbene derivative (2-(3',5'-bis(trifluoromethyl)-biphenyl-4-yl)-3-(4-(pyridin-4-yl)phenyl)acrylonitrile, CF3-CN-Py). The former emits blue emission, while the latter emits green emission. Different crystallization environments contribute to the adjustable morphologies. Then, novel cocrystals are fabricated with the introduction of 1,4-diiodotetrafluorobenzene (FDIB) to CF3-CN-Py. Both molecular conformation and packing are totally changed in the cocrystal system. Such cocrystal displays a 1D sky-blue emissive rod shape on account of a long-range ordered π-stacking of molecules. In addition, the 2D plate crystal and 1D rod cocrystal are further applied to optical waveguides. In the plate crystal, a packing of transition dipole moment (µ) inclined to the upper surface leads to an anisotropic optical waveguide. In the cocrystal, owing to the nearly horizontal µ orientation, the cocrystal exhibits light propagation along the primary growth direction and a low optical loss coefficient. The present study supplies an effective way to construct materials with controlled morphology and optical waveguide.

Poly(3-hexylthiophene)s Functionalized with N-Heterocyclic Carbenes as Robust and Conductive Ligands for the Stabilization of Gold Nanoparticles.

Recently, N-heterocyclic carbenes (NHCs) are explored as anchor groups to bind organic ligands to colloidal gold (i.e. gold nanoparticles, Au NPs), yet these efforts are confined to non-conjugated ligands so far-that is, focused solely on exploiting the stability aspect. Using NHCs to link Au NPs and electronically active organic components, for example, conjugated polymers (CPs), will allow capitalizing on both the stability as well as the inherent conductivity of the NHC anchors. Here, we report three types of Br-NHC-Au-X (X=Cl, Br) complexes, which, when used as starting points for Kumada polymerizations, yield regioregular poly(3-hexylthiophenes)-NHC-Au (P3HTs-NHC-Au) with narrow molecular weight distributions. The corresponding NPs are obtained via direct reduction and show excellent thermal as well as redox stability. The NHC anchors enable electron delocalization over the gold/CP interface, resulting in an improved electrochromic response behavior in comparison with P3HT-NHC-Au.

Carbonized Polymer Dots with Tunable Room-Temperature Phosphorescence Lifetime and Wavelength.

Recently, the room-temperature phosphorescence (RTP) properties of carbon dots (CDs) have attracted significant interest. However, the regulation of RTP emission faces great challenges because of untunable emissive lifetime and wavelength. Here, ultrahigh-yield acrylamide-based N-doped carbonized polymer dots (AN-CPDs) with ultralong RTP lifetime are synthesized by a one-step hydrothermal addition polymerization and carbonization strategy. The RTP lifetime and wavelength of the proposed AN-CPDs can be regulated by changing the carbonization degree. Thus, the AN-CPDs' RTP lifetimes are in the range of 61.4-466.5 ms, while the RTP emission wavelengths vary from 485 to 558 nm. Further experiment and theoretical calculation proved that RTP can be attributed to the polymer/carbon hybrid structure and nitrous functional groups as the molecular state related emission centers. Supramolecular cross-linking in the aggregated state is vital for the RTP emission of the AN-CPDs by restricting the nonradiative transition of the triplet excitons. AN-CPDs of different RTP lifetimes can be applied to time-resolved multistage information encryption and multistage anticounterfeiting. This work facilitates the optical regulation and application potential of CDs and provides profound insights into the effect of the polymer/carbon hybrid structure on the properties of CDs.

The reaction mechanism and selectivity of acetylene hydrogenation over Ni-Ga intermetallic compound catalysts: a density functional theory study.

Intermetallic compounds (IMCs) have shown excellent catalytic performance toward the selective hydrogenation of acetylene, but the theoretical understanding on this reaction over Ni-based IMCs is rather limited. In this work, the adsorptions of the C2 species, Bader charge, projected density of states (PDOS) and the reaction pathways were calculated by the density functional theory (DFT) method to investigate the mechanism and selectivity for the acetylene hydrogenation on the (111) surface of NinGa (n = 1, 3) IMCs, with a comparative study on the pristine Ni(111) surface. The results indicate that the adsorption energy of acetylene increased along with the Ni/Ga ratio, therefore a feasible acetylene adsorption on the Ga-rich surface guaranteed a low effective barrier, leading to the best activity for the NiGa(111) surface among three surfaces. Bader charge analysis shows that electrons transferred from Ga atoms to Ni atoms and further delivered to C2 species, decreasing the adsorption capacity of C2 species on NiGa(111) in comparison with those on Ni(111) and Ni3Ga(111). The reaction pathway of acetylene hydrogenation to ethylene via vinyl or even over-hydrogenation to ethane via ethyl is more favorable than the pathway involving the ethylidene intermediate on all surfaces. Moreover, the ethylene selectivity has a positive correlation with the gallium content by comparing the desorption barrier with the hydrogenation barrier of ethylene, thus the NiGa(111) surface also exhibits the best selectivity. Therefore, the NiGa(111) surface demonstrates to be an excellent reaction facet for the semihydrogenation of acetylene, which agreed with the experimental findings, and would provide helpful instructions for designing and preparing highly-selective and noble-substitute catalysts of alkyne semihydrogenation.

DFT-Based Simulation and Experimental Validation of the Topotactic Transformation of MgAl Layered Double Hydroxides.

The thermal topotactic transformation mechanism of MgAl layered double hydroxides (LDHs) is investigated by a combined theoretical and experimental study. Thermogravimetric differential thermal analysis (TG-DTA) results reveal that the LDH phase undergoes four key endothermic events at 230, 330, 450, and 800 °C. DFT calculations show that the LDH decomposes into CO2 and residual O atoms via a monodentate intermediate at 330 °C. At 450 °C, the metal cations almost maintain their original distribution within the LDH(001) facet during the thermal dehydration process, but migrate substantially along the c-axis direction perpendicular to the (001) facet; this indicates that the metal arrangement/dispersion in the LDH matrix is maintained two-dimensionally. A complete collapse of the layered structure occurs at 800 °C, which results in a totally disordered cation distribution and many holes in the final product. The structures of the simulated intermediates are highly consistent with the observed in situ powder XRD data for the MgAl LDH sample calcined at the corresponding temperatures. Understanding the structural topotactic transformation process of LDHs would provide helpful information for the design and preparation of metal/metal oxides functional materials derived from LDH precursors.

Delayed fluorescence in a solution-processable pure red molecular organic emitter based on dithienylbenzothiadiazole: a joint optical, electroluminescence, and magnetoelectroluminescence study.

The discovery of triplet excitons participating in the photoluminescent processes in a growing number of pure organic emitters represents an exciting impetus for a diversity of promising opto, bio, and optoelectronic applications. In this contribution, we have studied a small-molecule dithienylbenzothiadiazole-based red-emitting dye red-1b, which shows clearly delayed fluorescence under optical and electrical excitation. The OLED device that contained red-1b as a nondoped solution-processable emitter exhibited a moderately high utilization of exciton amounting to ≈31% and slow efficiency roll-off. Magnetoelectroluminescence measurements revealed the coexistence of reverse intersystem crossing from the lowest triplet state to singlet state (RISC, E-type triplet to singlet up-conversion) and triplet-triplet annihilation (TTA, P-type triplet to singlet up-conversion). Specifically, in low current-density regime, the moderately high exciton utilization is attributed to RISC (i.e., thermally activated delayed fluorescence, TADF), whereas in high current-density regime, TTA may contribute to suppressing efficiency roll-off. Furthermore, the results showed that red-1b may represent a new kind of organic red emitters that display delayed fluorescence in a way differing from the few red emitters investigated so far.