Donor-Acceptor Copolymers with 9-(2-Ethylhexyl)carbazole or Dibenzothiophene-5,5-dioxide Donor Units and 5,6-Difluorobenzo[c][1,2,5]thiadiazole Acceptor Units for Photonics.

Semiconducting polymers, particularly of the third generation, including donor-acceptor (D-A) copolymers, are extensively studied due to their huge potential for photonic and electronic applications. Here, we report on two new D-A copolymers, CP1 and CP2, composed of different electron-donor (D) units: 9-(2-ethylhexyl)carbazole or dibenzothiophene-5,5-dioxide, respectively, and of 4,7-bis(4'-(2-octyldodecyl)thiophen-2'-yl)-5,6-difluorobenzo[c][1,2,5]thiadiazole building block with central 5,6-difluorobenzo[c][1,2,5]thiadiazole electron-acceptor (A) units, which were synthesized by Suzuki coupling in the high-boiling solvent xylene and characterized. The copolymers exhibited very good thermal and oxidation stability. A copolymer CP1 with different molecular weights was prepared in order to facilitate a comparison of CP1 with CP2 of comparable molecular weight and to reveal the relationship between molecular weight and properties. The photophysical, electrochemical, and electroluminescence properties were examined. Intense red photoluminescence (PL) with higher PL efficiencies for CP1 than for CP2 was observed in both solutions and films. Red shifts in the PL thin film spectra compared with the PL solution spectra indicated aggregate formation in the solid state. X-ray diffraction measurements revealed differences in the arrangement of molecules in thin films depending on the molecular weight of the copolymers. Light-emitting devices with efficient red emission and low onset voltages were prepared and characterized.

Carbazole-Fluorene Copolymers with Various Substituents at the Carbazole Nitrogen: Structure-Properties Relationship.

Carbazole derivatives, carbazole-containing polymers and iridium complexes are of interest due to many possible applications in photonics, electronics and biology, particularly as active or hole-transporting layers in organic as well as perovskite devices due to their interesting properties. Here, a series of carbazole-fluorene conjugated copolymers with various substituents at the N-carbazole position (2-methoxycarbonylethyl, 2-carboxyethyl, 2-ethylhexyl, and nonan-2,4-dionatoiridium(III)bis(2-phenylpyridine-N,C2')-9-yl) was prepared by Suzuki coupling. Their photophysical, electrochemical and electroluminescence (EL) properties were studied. Effects of molecular weight and substituents attached to carbazole unit on their properties are reported. The carbazole-fluorene copolymers in dilute solutions exhibited intense photoluminescence (PL) emission in the blue spectral region with high PL quantum yields (78-87%) except for the copolymer with the iridium complex (23%). Similar PL spectra were observed in dilute solutions. More pronounced differences were found in thin film PL and EL properties due to excimer/aggregate formation. Light-emitting devices (LEDs) made of copolymers with 2-ethylhexyl as N-carbazole substituent exhibited efficient EL emission with the best performance and the lowest EL onset voltages (3-4 V), while the LEDs made of copolymers with other substituents were not as efficient, but showed anomalous behavior and memory effects in current-voltage characteristics promising also for bio-inspired electronics.

Effects of the Donor Unit on the Formation of Hybrid Layers of Donor-Acceptor Copolymers with Silver Nanoparticles.

Donor-acceptor (D-A) copolymers containing perylene-3,4,9,10-tetracarboxydiimide (PDI) electron-acceptor (A) units belonging to n-type semiconductors are of interest due to their many potential applications in photonics, particularly for electron-transporting layers in all-polymeric or perovskite solar cells. Combining D-A copolymers and silver nanoparticles (Ag-NPs) can further improve material properties and device performances. Hybrid layers of D-A copolymers containing PDI units and different electron-donor (D) units (9-(2-ethylhexyl)carbazole or 9,9-dioctylfluorene) with Ag-NPs were prepared electrochemically during the reduction of pristine copolymer layers. The formation of hybrid layers with Ag-NP coverage was monitored by in-situ measurement of absorption spectra. The Ag-NP coverage of up to 41% was higher in hybrid layers made of copolymer with 9-(2-ethylhexyl)carbazole D units than in those made of copolymer with 9,9-dioctylfluorene D units. The pristine and hybrid copolymer layers were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy, which proved the formation of hybrid layers with stable Ag-NPs in the metallic state with average diameters <70 nm. The influence of D units on Ag-NP diameters and coverage was revealed.

Formamidinium Lead Iodide Perovskite Thin Films Formed by Two-Step Sequential Method: Solvent-Morphology Relationship.

Thin films made of formamidinium lead iodide (FAPbI3) perovskites prepared by a two-step sequential deposition method using various solvents for formamidinium iodide (FAI) - isopropanol, n-butanol and tert-butanol, were studied with the aim of finding a correlation between morphology and solvent properties to improve film quality. They were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) and their photophysical properties were studied by means of absorption and photoluminescence (PL) spectroscopies. XRD patterns, absorption and PL spectra proved α-phase formation for all selected solvents. An excessive amount of PbI2 found in perovskite films prepared with n-butanol indicates incomplete conversion. Thin film morphology, such as grain and crystallite size, depended on the solvent. Using tert-butanol, thin films with a very large grain size of up to several micrometers and with preferred crystallite orientation were fabricated. The grain size increased as follows: 0.2-0.5, 0.2-1 and 2-5 µm for isopropanol, n-butanol and tert-butanol, respectively. A correlation between the grain size and viscosity, electric permittivity and polarizability of the solvent could be considered. Our results, including fabrication of perovskite films with large grains and fewer grain boundaries, are important and of interest for many optoelectronic applications.

Hybrid Layers of Donor-Acceptor Copolymers with Homogenous Silver Nanoparticle Coverage for Photonic Applications.

Hybrid layers of donor-acceptor (D-A) copolymers containing N,N'-dialkylperylene-3,4,9,10-tetracarboxydiimide electron-acceptor units covered with silver nanoparticles (Ag-NPs) were prepared by electrochemical doping of pristine layers during reduction processes. In situ optical absorption spectra of the layers were recorded during the formation of Ag-NP coverage. The hybrid layers were characterized by absorption spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDX). In the absorption spectra of the hybrid layers, a surface plasmon band characteristic of Ag-NPs appeared. Significant improvements in light absorption due to the plasmonic effects of Ag NPs were observed. Stable Ag-NPs with an average diameter of 41-63 nm were formed on the surface, as proven by SEM and XPS. The Ag-NP coverage and size depended on the hybrid layer preparation conditions and on the copolymer composition. The metallic character of the Ag-NPs was proven by XPS. The location in the surface layer was further confirmed by EDX analysis. To the best of our knowledge, this is the first report on such hybrid layers having the potential for a variety of photonic and electronic applications.

Synthesis and Photophysical and Electroluminescent Properties of Poly(1,4-phenylene-ethynylene)-alt-poly(1,4-phenylene-vinylene)s with Various Dissymmetric Substitution of Alkoxy Side Chains.

The synthesis and characterization of a set of conjugated polymers, poly(1,4-phenylene-ethynylene)-alt-poly(1,4-phenylene-vinylene)s (PPE-PPVs), with a dissymmetrical configuration (partial or total) of alkoxy side chains is reported. Five new polymers bearing octyloxy and/or octadecyloxy side chains at the phenylene-ethynylene and phenylene-vinylene segments, respectively, were obtained. Two symmetrical substituted polymers were used for comparison. Polymers with weight-average molecular weight, Mw, up to 430 000 g/mol and degree of polymerization between 17 and 322 were obtained by a Horner-Wadsworth-Emmons olefination polycondensation reaction of the respective luminophoric dialdehydes and bisphosphonates. As expected, identical conjugated backbones in all polymers results in very similar photophysical response in dilute solution, with high fluorescence quantum yields between 50% and 80%. In contrast, the thin film properties are dependent on the combinatorial effects of side chain configuration, molecular weight, and film thickness parameters, which are the basis of the resulting comparison and discussion.

Stabilization of calcium- and terbium-carboxylate bonds by NH...O hydrogen bonds in a mononuclear complex: a functional model of the active site of calcium-binding proteins.

Novel benzoic acid ligands with bulky amide groups at the ortho position, 2,6-(MeCONH)(2)C(6)H(3)CO(2)H (1) and 2,6-(t-BuCONH)(2)C(6)H(3)CO(2)H (2), and their tris- and tetrakis(carboxylate) complexes with Ca(II) and Tb(III) ions, (NEt(4))(2)[Ca(II)[O(2)C-2,6-(t-BuCONH)(2)C(6)H(3)](4)] (4), [Tb[O(2)C-2,6-(t-BuNHCO)(2)C(6)H(3)](3)(H(2)O)(3)]] (5), and (NMe)(4)[Tb[O(2)C-2,6-(t-BuNHCO)(2)C(6)H(3)](4)(thf)] (6), were synthesized. The formation of the NH...O hydrogen bonds between the amide NH and carboxylate for 2, (NEt(4))[2,6-(t-BuCONH)(2)C(6)H(3)CO(2)] (3), and 4 was determined by (1)H NMR spectroscopy in solution and in the solid state (CRAMPS, IR). The ligand exchange reactions were attempted between 4 and a large excess of 2,4,6- Me(3)C(6)H(3)CO(2)H in chloroform-d solution; however, exchange reaction did not take place, indicating that the Ca(II) ions bound strongly to the carboxylate in 4. The Ca(II) ion binding properties with the benzoate derivatives were also examined using Tb(III) ion as a fluorescence probe. These results indicate that the NH...O hydrogen bonding between the amide NH and the oxygen atom of the carboxylate contributes to strong Ca(II) binding and prevents the dissociation of the calcium-carboxylate bond. The X-ray structural analyses of these complexes revealed that the NH.O hydrogen-bonded carboxylate ligands prefer the chelate-type coordination and create a mononuclear [Ca(O(2)CR)(4)](2)(-) or [Tb(O(2)CR)(4)](-) core with anionic charge, which is known only in the active site of calcium-binding proteins.