Ultrafast Structure and Dynamics in the Thermally Activated Delayed Fluorescence of a Carbene-Metal-Amide

Thermally activated delayed fluorescence has enormous potential for the development of efficient light emitting diodes. A recently discovered class of molecules (the carbene – metal – amides, CMAs) are exceptionally promising as they combine the small singlet - triplet energy gap required for thermal activation with a large transition moment for emission. Calculations suggest that excited state structural dynamics modulate the critical coupling between singlet and triplet states, but do not agree on the nature of those dynamics. Here we report ultrafast time resolved transient absorption and Raman studies of CMA photodynamics. The measurements reveal complex structural evolution following intersystem crossing on the tens to hundreds of picoseconds timescale, and a change in the low frequency vibrational spectrum between singlet and triplet states. The latter is assigned to a change in frequency or amplitude associated with a Raman active mode localized on the metal centre

Organic persistent room temperature phosphorescence enabled by carbazole impurity

The molecular design of metal-free organic phosphors is essential for realizing persistent room-temperature phosphorescence (pRTP) despite its spin-forbidden nature. A series of halobenzonitrile–carbazoles has been prepared following a one-pot nucleophilic substitution protocol involving commercially available and laboratory-synthesized carbazoles. We demonstrate how halo- and cyano-substituents affect the molecular geometry in the crystal lattice, resulting in tilt and/or twist of the carbazole with respect to the phenyl moiety. Compounds obtained from the commercially available carbazole result in efficient pRTP of organic phosphors with a high quantum yield of up to 22% and a long excited state lifetime of up to 0.22 s. Compounds obtained from the laboratory-synthesized carbazole exhibit thermally activated delayed fluorescence with an excited state lifetime in the millisecond range. In-depth photophysical studies reveal that luminescence originates from the mixed locally excited state (3LE, nπ*)/charge transfer state

Highly photoluminescent copper carbene complexes based on prompt rather than delayed fluorescence

Linear two-coordinate copper complexes of cyclic (alkyl)(amino)-carbenes (CAAC)CuX (X = halide) show photoluminescence with solid-state quantum yields of up to 96%; in contrast to previously reported Cu photoemitters the emission is independent of temperature over the range T = 4 – 300 K and occurs very efficiently by prompt rather than delayed fluorescence, with lifetimes in the sub-nanosecond range

Synthesis, structure and cytotoxicity of cyclic (alkyl)(amino) carbene and acyclic carbene complexes of group 11 metals

A series of complexes of cyclic (alkyl)(amino)carbene (CAAC) complexes of copper, silver and gold have been investigated for their antiproliferative properties. A second series of acyclic carbene (ACC) complexes of gold(I) were prepared by nucleophilic attack on isocyanide complexes by amines and amino esters, to give (ACC)AuCl, [(ACC)Au(PTA)]+ (PTA = triazaphosphaadamantane), as well as mixed-carbene compounds [(CAAC)Au(ACC)]+. Representative complexes were characterised by X-ray diffraction which confirmed the mononuclear linear structures without close intermolecular contacts or aurophilic interactions. The redox properties of these complexes have been determined. The compounds were tested against a panel of human cancer cell lines including leukemia (HL 60), breast adenocarcinoma cells (MCF-7) and human lung adenocarcinoma epithelial cell lines (A549), which show varying degrees of cisplatin resistance. The pro-ligand iminium salts and the PTA complexes were non-toxic. By contrast, the CAAC complexes show high cytotoxicity, with IC50 values in the sub-micromolar to ∼100 nanomolar range, even against cisplatin-insensitive MCF-7 and A549 cells. Cationic bis-carbene complexes [(Me2CAAC)2M]+ (6–8, M = Cu, Ag and Au) proved particularly effective. The mechanism of cell growth control by these complexes remains to be established, although possible modes of action such as inhibition of thioredoxin reductase (TrxR), which is a common pathway for gold NHC compounds, or the formation of reactive oxygen species (ROS) through redox processes, could be ruled out as primary pathways

Synthesis, structures and photoluminescence properties of silver complexes of cyclic (alkyl)(amino)carbenes

Silver complexes of cyclic (alkyl)(amino)carbenes (CAACs), (RL)nAgX (n = 1, X = Cl, Br, I; n = 2, X = OTf; R = Me2, Et2, or adamantyl) are accessible in high yields by reacting free carbenes with silver salts. The smaller carbene ligand Me2L leads to the formation of a mixture of neutral (Me2L)AgCl and cationic [(Me2L)2Ag]+ products. The transmetallation of (AdL)AgCl with copper and gold halides gives the corresponding copper and gold compounds (AdL)MCl (M = Cu and Au) in a clean and quantitative reaction. Whereas (Me2L)AgCl is monomeric in the solid state, (Et2L)AgCl crystallizes as a Cl-bridged dimer. None of the compounds show metal-metal interactions. The complexes show blue photoluminescence, which consists of a fluorescence component with a lifetime of several nanoseconds, as well as a long-lived emission in the microsecond regime

The Interrelation Between Hardiness and Prognostic Potential of Students of Higher Education Institutions

The paper presents the results of an empirical study of specific features and the relationship between hardiness of students and prognostic potential of their personality. The methods of research comprised: theoretical analysis, empirical research (testing), qualitative analysis of the obtained data, mathematical and statistical data processing (SPSS Statistics, Excel). It has been found that students with a high level of prognostic potential development are distinguished by pronounced personality traits typical of hardy people. The authors have proved in the paper that the prognostic potential of students is a holistic system of personality resources, which is based on specific features of thinking and building a secondary image. There are criteria and development levels of the prognostic potential among students: an internal criterion (features of thinking and building secondary images) and an external criterion (the effectiveness of forecasting activities, the conformity of the stages of prognostic activity with the reference model). The prognostic potential is interconnected with personal and professional characteristics of students (features of the intellectual, communicative, emotional-volitional and motivation spheres). There are significant differences between students with different levels of development of prognostic potential according to the main personal and professional features. The correlation analysis of the data gave the following interrelations: there is a direct interrelationship between the level of development of prognostic potential and emotional stability of students; between the level of development of prognostic potential and such motives for studying at a university as professional and educational-cognitive motives; between the level of development of prognostic potential and the features of self-regulation. On the basis of the results of an empirical study, the authors designed a program for the prognostic potential development of students which includes active teaching methods, lectures, and trainings

Polar optical phonons in wurtzite spheroidal quantum dots: Theory and application to ZnO and ZnO/MgZnO nanostructures

Polar optical-phonon modes are derived analytically for spheroidal quantum dots with wurtzite crystal structure. The developed theory is applied to a freestanding spheroidal ZnO quantum dot and to a spheroidal ZnO quantum dot embedded into a MgZnO crystal. The wurtzite (anisotropic) quantum dots are shown to have strongly different polar optical-phonon modes in comparison with zincblende (isotropic) quantum dots. The obtained results allow one to explain and accurately predict phonon peaks in the Raman spectra of wurtzite nanocrystals, nanorods (prolate spheroids), and epitaxial quantum dots (oblate spheroids).Comment: 11 page