Effect of aggregation on thermally activated delayed fluorescence and ultralong organic phosphorescence:QM/MM study

Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the explanation of the luminescent properties of(R)-5-(9H-carbazol-9-yl)-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione((R)-ImNCz),which was recently reported[Chemical Engineering Journal 418129167(2021)].The polarizable continuum model(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method are adopted in simulation of the property of the molecule in the gas phase,solvated in acetonitrile and in aggregation states.It is found that large spin–orbit coupling(SOC)constants and a smaller energy gap between the first singlet excited state and the first triplet excited state(△E_(st))in prism-like single crystals(SC_(p)-form)are responsible for the TADF of(R)-lmNCz,while no TADF is found in block-like single crystals(SC_(b)-form)with a larger △E_(st).The multiple ultralong phosphorescence(UOP)peaks in the spectrum are of complex origins,and they are related not only to ImNCz but also to a minor amount of impurities(ImNBd)in the crystal prepared in the laboratory.The dimer has similar phosphorescence emission wavelengths to the(R)-lmNCz-SC_(p) monomers.The complex composed of(R)-lmNCz and(R)-lmNBd contributes to the phosphorescent emission peak at about 600 nm,and the phosphorescent emission peak at about 650 nm is generated by(R)-lmNBd.This indicates that the impurity could also contribute to emission in molecular crystals.The present calculations clarify the relationship between the molecular aggregation and the light-emitting properties of the TADF emitters and will therefore be helpful for the design of potentially more useful TADF emitters.

Bulk nanocrystalline Al prepared by cryomilling

Bulk nanocrystalline Al was fabricated by mechanically milling at cryogenic temperature （cryomilling） and then by hot pressing in vacuum. By using X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and transmission electron microscopy （TEM）, the microstructure evolution of the material during cryomilling and consolidation was investigated. With increasing the milling time, the grain size decreased sharply and reduced to 42 nm when cryomilled for 12 h. The grains had grown up, and the columnar grain was formed under the hot pressing and extrusion compared with the cryomilled powders. The grain size of as-extruded specimen was approximately 300-500 nm. The reason of high thermal stability of this bulk was attributed primarily to the Zener pinning from the grain boundary of the AlN arising from cryomilling and the solute drag of the impurity. Tensile tests show that the strength of nanocrystalline Al is enhanced with decreasing grain size. The ultimate tensile strength and tensile elongation were 173 MPa and 17.5%, respectively. It appears that the measured high strength in the cryomilled Al is related to a grain-size effect, dispersion strengthening, and dislocation strengthening.

Perspective for aggregation-induced delayed fluorescence mechanism:A QM/MM study

To enhance the potential application of thermally activated delayed fluorescence(TADF)molecular materials,new functions are gradually cooperated to the TADF molecules.Aggregation induced emission can effectively solve the fluorescence quenching problem for TADF molecules in solid phase,thus aggregation-induced delayed fluorescence(AIDF)molecules were recently focused.Nevertheless,their luminescent mechanisms are not clear enough.In this work,excited state properties of an AIDF molecule DMF-BP-DMAC[reported in Chemistry-An Asian Journal 14828(2019)]are theoretically studied in tetrahydrofuran(THF)and solid phase.For consideration of surrounding environment,the polarizable continuum method(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method were applied for solvent and solid phase,respectively.Due to the increase of the transition dipole moment and decrease of the energy difference between the first single excited state(S1)and the ground state(S0),the radiative rate is increased by about 2 orders of magnitude in solid phase.The energy dissipation of the non-radiative process from S1 to S0 is mainly contributed by low-frequency vibrational modes in solvent,and they can be effectively suppressed in aggregation,which may lead to a slow non-radiation process in solid phase.Both factors would induce enhanced luminescence efficiency of DMF-BP-DMAC in solid phase.Meanwhile,the small energy gap between S1 and triplet excited states results in high reverse intersystem crossing(RISC)rates in both solvent and solid phase.Therefore,TADF is confirmed in both phases.Aggregation significantly influences both the ISC and RISC processes and more RISC channels are involved in solid state.The enhanced delayed fluorescence should be induced by both the enhanced fluorescent efficiency and ISC efficiency.Our calculation provides a reasonable explanation for experimental measurements and helps one to better understand the luminescence mechanism of AIDF molecules.

18F-FDG PET/CT与增强CT在成人原发前纵隔恶性肿瘤中的诊断价值

目的探讨18F-氟脱氧葡萄糖(FDG)PET/CT与增强CT在成人原发前纵隔恶性肿瘤中的诊断价值,以提高对该部位病变的诊断水平。方法回顾性分析2016年6月至2019年5月在湖北文理学院附属医院(襄阳市中心医院)经病理证实的成人原发前纵隔肿瘤患者80例(恶性肿瘤35例、良性肿瘤45例),其中,男性46例、女性34例,年龄20~80(45.5±10.2)岁。所有患者均行全身18F-FDG PET/CT及胸部CT平扫+增强扫描,2种检查的间隔时间在2周内。分别计算并采用χ2检验比较18F-FDG PET/CT与增强CT扫描的诊断灵敏度、特异度和准确率,采用χ2检验比较2种检查方法对不同类型恶性肿瘤的诊断效能。结果35例恶性肿瘤中胸腺癌15例,淋巴瘤10例,恶性生殖细胞瘤7例,神经内分泌癌、恶性黑色素瘤及滑膜肉瘤各1例。18F-FDG PET/CT诊断成人原发前纵隔恶性肿瘤的灵敏度[97.1%(34/35)]、特异度[93.3%(42/45)]及准确率[95.0%(76/80)]均高于增强CT[71.4%(25/35)、77.8%(35/45)、75.0%(60/80)],且差异有统计学意义(χ2=8.612、4.357、12.471,均P<0.05);18F-FDG PET/CT对胸腺癌、淋巴瘤及恶性生殖细胞瘤诊断的准确率[93.3%(14/15)、100.0%(10/10)、85.7%(6/7)]均高于增强CT[60.0%(9/15)、50.0%(5/10)、28.6%(2/7)],且差异有统计学意义(χ2=4.503、6.333、4.333,均P<0.05)。结论18F-FDG PET/CT对成人原发前纵隔恶性肿瘤具有重要的诊断价值,其诊断效能优于增强CT,可作为该病主要的检查方法。

Tensile and Fracture Properties of 15 vol% SiC_p/2009Al Composites Fabricated by Hot Isostatic Pressing and Hot Extrusion Processes

15 vol% silicon carbide particle （SiCp）-reinforced 2009A1 matrix （15 vol% SiCp/2009A1） composites were fabricated by hot isostatic pressing （HIP） and hot extrusion processes. The tensile and fracture properties of 15 vol% SiCp/ 2009Al were studied. The results showed that hot extrusion increased the ultimate tensile strength （UTS）, yield strength （YS）, elongation （EL）, reduction in area （RA）, and fracture toughness of the composites. The heat treatment resulted in the increase in UTS, YS, and fracture toughness, but a decrease in EL and RA. Both hot extrusion and heat treatment had negligible effects on elastic modulus （E）. With the increase of SiCp size, the UTS, YS, and E decreased, but the EL and RA increased. The fracture toughness increased first and then decreased with increasing SiCp size, and when the SiCp size was about 7 μm, the composites obtained the maximum fracture toughness value of 31.74 MPa m^1/2.

Luminescent Cu(Ⅰ) and Ag(Ⅰ) coordination polymers:Fast phosphorescence or thermally activated delayed fluorescence

By applying two donor-acceptor motif molecules,5,10-di(pyridin-4-yl)-5,10-dihydrophenazine(L1)and 10,10'-di(pyridin-3-yl)-10H,10'H-9,9'-spiroacridine(L2),as ligands and CuI/AgCF3CO2 as metal salt,we synthesized three coordination polymers,namely,{Cu4(L1)2I4}(CP1),{Cu(L2)I·CHCl3}(CP2)and{Ag(L2)CO2CF3·CHCl3}(CP3).X-ray crystallographic analysis revealed that three coordination polymers all feature one-dimensional(1D)linear chains which are consisting of molecular boxlike units.In comparison with low photoluminescence quantum yield(PLQY)of two ligands,three coordination polymers,CP1,CP2 and CP3,present more intense photoluminescence with PLQY of 15%,46%and 34%at room temperature respectively.The PL emission of CP1 and CP2 at room temperature could be attributed to the fast phosphorescence with lifetime both around 5 ms due to effective intersystem crossing(ISC).Whilst,it is worth noting that CP3 exhibit thermally activated delayed fluorescence(TADF)emission at room temperature.

Single-Component Color-Tunable Smart Organic Emitters with Simultaneous Multistage Stimuli-Responsiveness and Multimode Emissions

Achieving color-tunable emission in single-component organic emitters with multistage stimuli-responsiveness is of vital significance for intelligent optoelectronic applications,but remains enormously challenging.Herein,we present an unprecedented example of a color-tunable single-component smart organic emitter(DDOP)that simultaneously exhibits multistage stimuli-responsiveness and multimode emissions.DDOP based on a highly twisted amide-bridged donor-tcceptor-donor structure has been found to facilitate intersystem crossing,form multimode emissions,and generate multiple emissive species with multistage stimuli-responsiveness.DDOP pristine crystalline powders exhibit abnormal excitation-dependent emissions from a monomer-dominated blue emission centered at 470 nm to a dimer-dominated yellow emission centered at 550 nm through decreasing the ultraviolet(UV)excitation wavelengths,whereas DDOP single crystals show a wide emission band with a main emission peak at 585 nm when excited at different wavelengths.The emission behaviors of pristine crystalline powders and single crystals are different,demonstrating emission features that are closely related to the aggregation states.The work has developed color-tunable single-component organic emitters with simultaneous multistage stimuli-responsiveness and multimode emissions,which is vital for expanding intelligent optoelectronic applications,including multilevel information encryption,multicolor emissive patterns,and visual monitoring of UV wavelengths.