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We report on the first case of the use of nonstoichiometric ternary (Ag–In–Zn–S) semiconductor nanocrystals as photoinitiators and photocatalysts of methyl methacrylate (MMA) polymerization. Two types of nanocrystals were tested, differing in their composition and characterized by red (λmax = 731 nm) and green (λmax = 528 nm) photoluminescence, respectively. Exploiting their reducing properties and capability of free radical generation we demonstrate that under ultraviolet (UV) radiation they effectively photoinitiate radical polymerization of MMA whereas under visible light (blue or green) they act as photocatalysts of living radical polymerization. [ABSTRACT FROM AUTHOR]

It is demonstrated that ternary Cu–Fe–S nanocrystals differing in composition (from Cu-rich to Fe-rich), structure (chalcopyrite or high bornite) and size can be obtained from a mixture of CuCl, FeCl3, thiourea and oleic acid (OA) in oleylamine (OLA) using the heating up procedure. This new preparation method yields the smallest Cu–Fe–S nanocrystals ever reported to date (1.5 nm for the high bornite structure and 2.7 nm for the chalcopyrite structure). A comparative study of nanocrystals of the same composition (Cu1.6Fe1.0S2.0) but different in size (2.7 nm and 9.3 nm) revealed a pronounced quantum confinement effect, confirmed by three different techniques: UV-vis spectroscopy, cyclic voltammetry and Mössbauer spectroscopy. The optical band gap increased from 0.60 eV in the bulk material to 0.69 eV in the nanocrystals of 9.3 nm size and to 1.39 eV in nanocrystals of 2.7 nm size. The same trend was observed in the electrochemical band gaps, derived from cyclic voltammetry studies (band gaps of 0.74 eV and 1.54 eV). The quantum effect was also manifested in Mössbauer spectroscopy by an abrupt change in the spectrum from a quadrupole doublet to a Zeeman sextet below 10 K, which could be interpreted in terms of the well defined energy states in these nanoparticles, resulting from quantum confinement. The Mössbauer spectroscopic data confirmed, in addition to the results of XPS spectroscopy, the co-existence of Fe(iii) and Fe(ii) in the synthesized nanocrystals. The organic shell composition was investigated by NMR (after dissolution of the inorganic core) and IR spectroscopy. Both methods identified oleylamine (OLA) and 1-octadecene (ODE) as surfacial ligands, the latter being formed in situ via an elimination–hydrogenation reaction occurring between OLA and the nanocrystal surface. [ABSTRACT FROM AUTHOR]

This critical review is devoted to semiconducting and high spin polymers which are of great scientific interest in view of further development of the organic electronics and the emerging organic spintronic fields. Diversified synthetic strategies are discussed in detail leading to high molecular mass compounds showing appropriate redox (ionization potential (IP), electron affinity (EA)), electronic (charge carrier mobility, conductivity), optoelectronic (electroluminescence, photoconductivity) and magnetic (magnetization, ferromagnetic spin interactions) properties and used as active components of devices such as n- and p-channel field effect transistors, ambipolar light emitting transistors, light emitting diodes, photovoltaic cells, photodiodes, magnetic photoswitches, etc. Solution processing procedures developed with the goal of depositing highly ordered and oriented films of these polymers are also described. This is completed by the description of principal methods that are used for characterizing these macromolecular compounds both in solution and in the solid state. These involve various spectroscopic methods (UV-vis-NIR, UPS, pulse EPR), electrochemistry and spectroelectrochemistry, magnetic measurements (SQUID), and structural and morphological investigations (X-ray diffraction, STM, AFM). Finally, four classes of polymers are discussed in detail with special emphasis on the results obtained in the past three years: (i) high IP, (ii) high ☋EA☋, (iii) low band gap and (iv) high spin ones. [ABSTRACT FROM AUTHOR]

New donor–acceptor conjugated alternating or random copolymers containing 1-methyl-2-phenylbenzimidazole and benzothiadiazole (P1), diketopyrrolopyrrole (P4), or both acceptors (P2) are reported. The specific feature of these copolymers is the presence of a permanent dipole-bearing moiety (1-methyl-2-phenyl imidazole (MPI)) fused with the 1,4-phenylene ring of the polymer main chain. For comparative reasons, polymers of the same main chain but deprived of the MPI group were prepared, namely, P5 with diketopyrrolopyrrole and P3 with both acceptors. The presence of the permanent dipole results in an increase of the optical band gap from 1.51 eV in P3 to 1.57 eV in P2 and from 1.49 eV in P5 to 1.55 eV in P4. It also has a measurable effect on the ionization potential (IP) and electrochemical band gap (EgCV), leading to their decrease from 5.00 and 1.83 eV in P3 to 4.92 and 1.79 eV in P2 as well as from 5.09 and 1.87 eV in P5 to 4.94 and 1.81 eV in P4. Moreover, the presence of permanent dipole lowers the exciton binding energy (Eb) from 0.32 eV in P3 to 0.22 eV in P2 and from 0.38 eV in P5 to 0.26 eV in P4. These dipole-induced changes in the polymer properties should be beneficial for photovoltaic applications. Bulk heterojunction solar cells fabricated from these polymers (with PC71BM acceptor) show low series resistance (rs), indicating good electrical transport properties. The measured power conversion efficiency (PCE) of 0.54% is limited by the unfavorable morphology of the active layer. [ABSTRACT FROM AUTHOR]

The sol–gel method was used to prepare amorphous TiO2 powders with sub-micrometric grain size. These powders together with commercial nanometric TiO2 were characterized with FT-IR spectroscopy, X-ray diffraction, scanning electron microscopy, and a light scattering method. Then electrorheological suspensions were composed out of these powders and their flow curves under electric field were recorded. The ER activity of the synthesized powders was relatively high which probably resulted from residual amounts of polar organic matter present in the prepared titania. It was found, however, that the studied suspensions underwent a very well pronounced agglomeration process clearly observed in suspensions of higher concentrations and particularly in those fluids which were exposed to electric field for some time. Therefore, the studied ERFs which were originally prepared out of nanometric powders contain in fact aggregated particles of considerably bigger size. The agglomeration process strongly influences all basic properties of the studied electrorheological suspensions. [ABSTRACT FROM AUTHOR]

This short critical review is devoted to the synthesis and functionalization of various types of azaacenes, organic semiconducting compounds which can be considered as promising materials for the fabrication of n-channel or ambipolar field effect transistors (FETs), components of active layers in light emitting diodes (LEDs), components of organic memory devices and others. Emphasis is put on the diversity of azaacenes preparation methods and the possibility of tuning their redox and spectroscopic properties by changing the C/N ratio, modifying the nitrogen atoms distribution mode, functionalization with electroaccepting or electrodonating groups and changing their molecular shape. Processability, structural features and degradation pathways of these compounds are also discussed. A unique feature of this review concerns the listed redox potentials of all discussed compounds which were normalized vs. Fc/Fc+. This required, in frequent cases, recalculation of the originally reported data in which these potentials were determined against different types of reference electrodes. The same applied to all reported electron affinities (EAs). EA values calculated using different methods were recalculated by applying the method of Sworakowski and co-workers (Org. Electron. 2016, 33, 300–310) to yield, for the first time, a set of normalized data, which could be directly compared. [ABSTRACT FROM AUTHOR]