Energetic Coordination Compounds: Investigation of Aliphatic Ligands and Development of Prototype Detonators.

In this work, energetic coordination compounds (ECCs) of transition metals (Fe, Ni, Cu, Zn) containing aliphatic amines as ligands were synthesized: ethylenediamine; 1,3-diaminopropane; tris(2-aminoethyl)amine; tris(3-aminopropyl)amine. The compounds were investigated in terms of ignition/explosion temperature, friction and impact sensitivity. For selected compounds, structural characterisation was presented (IR-ATR spectroscopy, Raman spectroscopy) and their morphology was determined (SEM, powder XRD). They were also investigated by differential scanning calorimetry (DSC). In order to assess the potential application of selected ECCs in detonators, underwater explosion tests were carried out, determining energetic performance. The results achieved for detonators containing ECCs were compared with those for reference detonators (containing pentaerythritol tetranitrate, PETN), indicating their potential use as a "green" alternative to nitric acid esters.

Naphthalene Phthalimide Derivatives as Model Compounds for Electrochromic Materials.

Electrochromism of organic compounds is a well-known phenomenon; however, nowadays, most research is focused on anodic coloring materials. Development of efficient, cathodic electrochromic materials is challenging due to the worse stability of electron accepting materials compared with electron donating ones. Nevertheless, designing stable cathodic coloring organic materials is highly desired-among other reasons-to increase the coloration performance. Hence, four phthalimide derivatives named 1,5-PhDI, 1,4-PhDI, 2,6-PhDI and 3,3'-PhDI were synthesized and analyzed in depth. In all cases, two imide groups were connected via naphthalene (1,5-PhDI, 1,4-PhDI, 2,6-PhDI) or 3,3'-dimethylnaphtidin (3,3'-PhDI) bridge. To observe the effect of chemical structure on physicochemical properties, various positions of imide bond were considered, namely, 1,5- 1,4- and 2,6-. Additionally, a compound with the pyromellitic diimide unit capped with two 1-naphtalene substituents was obtained. All compounds were studied in terms of their thermal behavior, using differential calorimetry (DSC) and thermogravimetric analysis (TGA). Moreover, electrochemical (CV, DPV) and spectroelectrochemical (UV-Vis and EPR) analyses were performed to evaluate the obtained materials in terms of their application as cathodic electrochromic materials. All obtained materials undergo reversible electrochemical reduction which leads to changes in their optical properties. In the case of imide derivatives, absorption bands related to both reduced and neutral forms are located in the UV region. However, importantly, the introduction of the 3,3'-dimethylnaphtidine bridge leads to a noticeable bathochromic shift of the reduced form absorption band of 3,3'-PhDI. This indicates that optimization of the phthalimide structure allows us to obtain stable, cathodic electrochromic materials.

2,1,3-Benzothiadiazole Small Donor Molecules: A DFT Study, Synthesis, and Optoelectronic Properties.

We herein report the design and synthesis of small-donor molecules, 2,1,3-benzothiadiazole derivatives (2a-d), by Stille or Suzuki reaction. The synthesized compounds were characterized by spectroscopic and electrochemical methods. The compounds 2a-d absorb the light in a wide range (the UV-green/yellow light (2c)) and emit from green to red/near IR light (2c). Furthermore, these compounds show a narrow energy gap (1.75-2.38 eV), and high Ea values increasing for polymers, which prove their electron-donating nature and semiconductor properties. The measurements were enhanced by theoretical modeling.

Effect of ß-Ketoiminato Ancillary Ligand Modification on Emissive Properties of New Iridium Complexes.

A series of new bis(benzo[h]quinolinato) Ir(III) complexes with modified ß-ketoiminato ancillary ligands were synthesized, and their electrochemical, photophysical properties were determined with the support of theoretical calculations. Moreover, all the synthesized heteroleptic Ir(III) complexes were examined as dopants of the host-guest type emissive layers in solution-processed phosphorescent organic light emitting diodes (PhOLEDs) of a simple structure. As expected on the basis of voltammetry measurements as well as DFT calculations, all the compounds appeared to be green emitters. Their examination showed that alteration of ß-ketoiminato ligand structure causes frontier orbitals' energy levels to be slightly changed, while significantly affecting photoluminescence and electroluminescence efficiencies of iridium phosphors containing these ligands. It was also found that modification of ancillary ligands might enhance charge trapping on the dopant, thus increasing its efficiency, especially in electroluminescence. From among the iridium complexes studied, the compound bearing 1-naphthyl group bonded to the nitrogen atom of the ancillary ligand proved to be the most efficient emitter. The PhOLED fabricated on the basis of this dopant has reached a luminance level of 16000 cd/m2, current efficiency close to 12 cd/A, and an external quantum efficiency around 3.2%.

Synthesis and Properties of New Dithienosilole Derivatives as Luminescent Materials.

Three new organosilicon compounds based on dithienosilole (DTSi) were synthesized in good yields. We report the optical and electrochemical properties of the resulting derivatives. We find that these compounds absorb the light in the ultraviolet and blue light range, and they exhibit luminescence in almost the entire range of visible light. After electropolymerization were significantly lowered, the values of the energy gap (even 1.51 eV for P2) and the ionization potential of the polymers were compared to monomers. Optoelectronic properties of the obtained compounds suggest that these derivatives of DTSi may be good candidates as the emissive layers in white organic light-emitting diodes (WOLEDs), which would reduce the amount of layers.

Spectroelectrochemistry of poly(3-hexylthiophenes) in solution.

ABSTRACT: The first comprehensive spectroelectrochemical account of the behaviour of regioregular (RR-P3HT) and statistical (ST-P3HT) poly(3-hexylthiophenes) in solution is presented, in contrast to the many reports dealing with P3HT films merely deposited from solution. The conducted experiments revealed that the two types of P3HTs behave in sharply different ways upon the application of electrochemical stimuli: ST-P3HT readily precipitates at mildly oxidative potentials, while the precipitation of the RR-P3HT takes place to a much lesser extent, even at higher potentials. The two polymers, studied via UV-Vis-NIR-EPR spectroelectrochemistry, exhibited properties mostly in line with earlier reports. Further study revealed that RR-P3HT largely remains in solution, even in its doped form, whereas only traces of the doped ST-P3HT are observed in solution in identical conditions. The high concentration of the doped RR-P3HT in solution can be explained by its ability to form soluble polymer agglomerates, in which the positive charge of the p-doped chains is stabilised by and delocalised over neighbouring, interacting undoped chains. These conclusions are consistent with SEM micrographs, which show that after cycling the potential of the electrode in a solution of ST-P3HT, a uniform layer is formed, covering most of the surface of the electrode, whereas in the case of RR-P3HT surface coverage is marginal and formed layer has the appearance of veined blotches.

Low and High Molecular Mass Dithienopyrrole-Naphthalene Bisimide Donor-Acceptor Compounds: Synthesis, Electrochemical and Spectroelectrochemical Behaviour.

Two low molecular weight electroactive donor-acceptor-donor (DAD)-type molecules are reported, namely naphthalene bisimide (NBI) symmetrically core-functionalized with dithienopyrrole (NBI-(DTP)2 ) and an asymmetric core-functionalized naphthalene bisimide with dithienopyrrole (DTP) substituent on one side and 2-ethylhexylamine on the other side (NBI-DTP-NHEtHex). Both compounds are characterized by low optical bandgaps (1.52 and 1.65 eV, respectively). NBI-(DTP)2 undergoes oxidative electropolymerization giving the electroactive polymer of ambipolar character. Its two-step reversible reduction and oxidation is corroborated by complementary EPR and UV/Vis-NIR spectroelectrochemical investigations. The polymer turned out to be electrochemically active not only in aprotic solvents but also in aqueous electrolytes, showing a distinct photocathodic current attributed to proton reduction. Additionally, poly(NBI-(DTP)2 ) was successfully tested as a photodiode material.

Doping-Induced Absorption Bands in P3HT: Polarons and Bipolarons.

In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p-type doping (oxidation) of the organic semiconductor poly(3- hexylthiophene-2,5-diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near-IR range as well as in the mid-IR range. In the low-oxidation regime, two absorption bands related to sub-gap transitions appear, one in the UV/Vis range and another one in the mid-IR range. The UV/Vis absorption gradually decreases upon further doping while the mid-IR absorption shifts to lower energy. Additionally, electron paramagnetic resonance (EPR) measurements are performed, showing an increase of the EPR signal up to a certain doping level, which significantly decreases upon further doping. Furthermore, the absorption spectra in the UV/Vis range are analyzed in relation to the morphology (crystalline vs. amorphous) by using theoretical models. Finally, the calculated charge carriers from cyclic voltammogram are linked together with optical transitions as well as with the EPR signals upon p-type doping. We stress that our results indicate the formation of polarons at low doping levels and the existence of bipolarons at high doping levels. The presented spectroscopic data are an experimental evidence of the formation of bipolarons in P3HT.

Electrochemically Induced Synthesis of Poly(2,6-carbazole).

The formation of a poly(2,6-carbazole) derivative during an electrochemical polymerization process is shown. Comparison of 3,5-bis(9-octyl-9H-carbazol-2-yl)pyridine and 3,5-bis(9-octyl-9H-carbazol-3-yl)pyridine by electrochemical and UV-Vis-NIR spectroelectrochemical measurements and DFT (density functional theory) calculation prove the formation of a poly(2,6-carbazole) derivative. Both of the compounds form stable and electroactive conjugated polymers.

Advances in star-shaped π-conjugated systems: properties and applications.

Until recently π-conjugated organic materials are based mainly on linear systems. Recent years, however, have brought about increasing interest in molecules boasting a dendritic, branched, or star-shaped architecture. This tendency is a direct result of the ongoing search for materials with progressively better properties. Such compounds, featuring novel, 3D architectures, exhibit a multitude of interesting qualities, making them stand out from well-known materials. The direction of star-shaped compound application is determined by whether they are able to form aggregates, π-stacks. This feature is a source of some astounding properties, coveted in numerous applications. Among this class of compounds high charge mobility, high fluorescence efficiency, and good charge separation are all found. Depending on the structure of the core, the molecule may adopt various types of symmetry. Similarly, the conjugation of orbitals may extend over the whole structure or be interrupted at chosen segments. The number of papers pertaining to star-shaped oligomers and polymers is ascending with each year, evidencing a growing interest in them. Consequently, this Review focuses particularly on the most recent reports concerning modification of the structure and properties of the aforementioned type of compounds, as well as on the development of devices based on them.

Investigating perimidine precursors for the synthesis of new multiredox polymers.

We present a new simple approach for electrochemical synthesis of semi-condensed ambipolar perinone polymers with phthaloperine (p1) or phenanthroline (p2) skeleton from available and cheap perimidine precursors. Polymerization of perimidine derivatives varies in efficiency depending on the monomer, but overall is highly efficient, especially when electropolymerization is used. Electrooxidation is well controllable and provides a certain characteristic share of new bonds in the structure of perimidine polymers: semi-ladder bis-perimidine unit, ladder bis-perimidine unit, and protonated bis-perimidine unit. Polymer p2 obtained with higher efficiency was put through broader analysis (UV-Vis, IR, ESR and quantum-chemical calculations). As indicated, donor-acceptor structure and specific intermolecular interactions of p2 assure its electrical conductivity and complex redox activity. Although protonated bonds break π-conjugation in the structure of the macromolecule, there is also a diradical state that favors intermolecular interactions and intermolecular π-conjugation channels within bis-perimidine segments. It has been proven that there is a diradical state which appears as an intermediate state between the oxidized and reduced states of the protonated polymer unit. This work positions perimidine polymers as a versatile ambipolar multiredox p- and n-type conductor, indicating a potential for expanding perinone-based perylene-diperimidine polymers for innovative electronics and (bio)sensors.

A Supramolecular Approach to Enhance the Optoelectronic Properties of P3HT-b-PEG Block Copolymer for Organic Field-Effect Transistors.

This study investigates a supramolecular approach to elucidate the interaction between an organic semiconducting molecule, specifically butyric acid-functionalized perylene diimide, and a block copolymer comprising poly-3-hexyl thiophene-b-polyethylene glycol. This interaction results in the formation of a precisely structured nanoarchitecture within the supramolecular block copolymer, driven by the ionic interplay between the block copolymer and small organic molecules. The optical properties of the synthesized supramolecular block copolymer were characterized by using ellipsometry. Additionally, further characterization employing atomic force microscopy, differential scanning calorimetry, and X-ray diffraction provided detailed insights into the crystallinity and morphology of the nanostructure. The characterization data showed that this approach significantly influenced the tuning of morphology, crystallinity, and optical and electronic properties of the resulting nanostructure. The demonstrated methodology holds considerable promise as a strategic tool for broadening the spectrum of attainable nanomorphologies in semiconducting polymers, particularly for applications in electronics or photovoltaics.

Exploring the Influence of P3HT on PTCA Crystallization and Phase Behavior in Thin Films.

The thermal properties and alignment of crystallinity of materials in thin films play crucial roles in the performance and reliability of various devices, especially in the fields of electronics, materials science, and engineering. The slight variations in the molecular packing of the active layer can make considerable differences in the optical and thermal properties. Herein, we aim to investigate the tuning of the physical properties of a blended thin film of n-type small organic molecules of perylene-3,4,9,10-tetracarboxylic acid (PTCA-SMs) with the mixing of the p-type polymer poly(3-hexylthiophene) (P3HT). The resulting thin films exhibit an enhanced surface crystallinity compared to the pristine material, leading to the formation of long crystallites, and these crystallites are thermally stable in the solid state, as confirmed by X-ray diffraction (XRD), atomic force microscopy (AFM), and thermal analysis using variable-temperature spectroscopic ellipsometry (VTSE) and differential scanning calorimetry (DSC). We believe that the crystalline structure of the obtained P3HT/PTCA-SMs blends is a combination of edge-on and face-on orientations, which enable the potential use of this material as an active layer in organic electronics.

N,N-Bis(9-methyl-3-carbazolyl)-4-anisidine as an Electroactive Material for Use in Perovskite Solar Cells.

Di(9-methyl-3-carbazolyl)-(4-anisyl)amine is presented as an effective hole-transporting material suitable for application in perovskite solar cells. It is obtained by a three-step synthesis from inexpensive starting compounds. It has a relatively high glass transition temperature of 93 °C and thermal stability with 5% weight loss at 374 °C. The compound exhibits reversible double-wave electrochemical oxidation below +1.5 V and polymerization at higher potential. A mechanism for its oxidation is proposed based on electrochemical impedance and electron spin resonance spectroscopy investigations, ultraviolet-visible-near-infrared absorption spectroelectrochemistry results, and density functional theory-based calculations. Vacuum-deposited films of the compound are characterized by a low ionization potential of 5.02 ± 0.06 eV and hole mobility of 10-3 cm2/(Vs) at an electric field of 4 × 105 V/cm. The newly synthesized compound has been used to fabricate dopant-free hole-transporting layers in perovskite solar cells. A power conversion efficiency of 15.5% was achieved in a preliminary study.

UV-vis and ECD spectroelectrochemistry of atropisomeric naphthalenediimide derivative.

The UV-vis and ECD spectroelectrochemistry (SEC) of a chiral binaphthalenylamine derivative of the N-butyl naphthalenediimide (NDIB-NH2) enantiomers were applied to measure UV-vis and ECD spectra of NDIB-NH2 radicals and dianion formed in the reduction and oxidation processes observed in cyclic voltammetry (CV). The CV curves and EPR spectroelectrochemistry enabled us to establish conditions at which a radical-anion [NDIB-NH2]̇.-, a dianion [NDIB-NH2]2-, and a radical-cation [NDIB-NH2]̇.+ are formed. The DFT restricted open-shell CAM-B3LYP-D3/def2TZVP/PCM calculations demonstrated that in the radical-anion [NDIB-NH2]̇.-, spin is spread over the NDI system while in the radical-cation [NDIB-NH2]̇+ it is spread over the aminonaphthalene moiety. The UV-vis spectra of radical-anion and dianion show the most significant changes in the 400-800 nm range. In that range, the ECD spectra varied with the change of electrode potential more than the UV-vis did and enabled the identification of a new ECD band of [NDIB-NH2]̇.- at ca. 400 nm hidden in the background in the UV spectra at -1000 mV. A broad structured ECD pattern with a maximum at ca. 530 nm was observed for [NDIB-NH2]̇.- (-1000 mV), while a single smooth ECD band of [NDIB-NH2]2- was located at 520 nm (-1750 mV). For the first time, an isosbestic point (455 nm) was found in ECD spectroelectrochemical measurements for the radical-cation [NDIB-NH2]̇.+ in equilibrium with the NDIB-NH2 neutral form. The TD-DFT CAM-B3LYP-D3/6-31G** calculations combined with the hybrid (explicit combined with implicit) solvation model fairly well reproduced the UV-vis and ECD SEC of neutral and redox forms of NDIB-NH2 but the ECD spectrum of [NDIB-NH2]̇.+ above 390 nm.

The Role of Electrochemical and Spectroelectrochemical Techniques in the Preparation and Characterization of Conjugated Polymers: From Polyaniline to Modern Organic Semiconductors.

This review article presents different electrochemical and spectroelectrochemical techniques used to investigate conjugated polymers. The development of this research area is presented from an over 40-year perspective-the period of research carried out by Professor Mieczyslaw Lapkowski. Initial research involved polymers derived from simple aromatic compounds, such as polyaniline. Since then, scientific advances in the field of conductive polymers have led to the development of so-called organic electronics. Electrochemical and spectroelectrochemical methods have a great influence in the development of organic semiconductors. Their potential for explaining many phenomena is discussed and the most relevant examples are provided.

Perinone-New Life of an Old Molecule.

A review of publications on the synthesis and properties of a family of compounds called perinones was carried out. The basic molecule has been known for several decades mainly as a photostable pigment, and in recent years it has become increasingly used in organic electronics. This paper describes the methods of synthesis of low molecular weight compounds and polymers based on that molecule; the basic spectroscopic, photochemical, electrochemical and electronic properties important for the construction of organic electronics and optoelectronics devices are also discussed.

ECD spectroelectrochemistry: A review.

The electronic circular dichroism (ECD) spectroscopy is probably the most important chiraloptical method, and the role of chirality in contemporary chemistry, pharmacy, and material science constantly increases. On the other hand, the electrochemical methods are also very sensitive tools for studying multivarious redox processes. Nevertheless, the first ECD spectroelectrochemical (SEC) study was only published by Daub, Salbeck and Aurbach in 1988, and since then, the ECD SEC method has been mentioned in only thirty papers. By the summer of 2020, the ECD SEC studies were mainly focused around molecular systems for organic, and marginally, inorganic chiroptical switching studies of biochemical redox reactions. The review provides more details about the ECD SEC studies carried out so far. At the end, we suggest some future applications for the ECD spectroelectrochemistry.

Electrochemical and Spectroelectrochemical Studies on the Reactivity of Perimidine-Carbazole-Thiophene Monomers towards the Formation of Multidimensional Macromolecules versus Stable π-Dimeric States.

During research on cross-linked conducting polymers, double-functionalized monomers were synthesized. Two subunits potentially able to undergo oxidative coupling were used-perimidine and, respectively, carbazole, 3,6-di(hexylthiophene)carbazole or 3,6-di(decyloxythiophene)carbazole; alkyl and alkoxy chains as groups supporting molecular ordering and 14H-benzo[4,5]isoquinone[2,1-a]perimidin-14-one segment promoting CH⋯O interactions and π-π stacking. Electrochemical, spectroelectrochemical, and density functional theory (DFT) studies have shown that potential-controlled oxidation enables polarization of a specific monomer subunit, thus allowing for simultaneous coupling via perimidine and/or carbazole, but mainly leading to dimer formation. The reason for this was the considerable stability of the dicationic and tetracationic π-dimers over covalent bonding. In the case of perimidine-3,6-di(hexylthiophene)carbazole, the polymer was not obtained due to the steric hindrance of the alkyl substituents preventing the coupling of the monomer radical cations. The only linear π-conjugated polymer was obtained through di(decyloxythiophene)carbazole segment from perimidine-di(decyloxythiophene)-carbazole precursor. Due to the significant difference in potentials between subsequent oxidation states of monomer, it was impossible to polarize the entire molecule, so that both directions of coupling could be equally favored. Subsequent oxidation of this polymer to polarize the side perimidine groups did not allow further crosslinking, because rather the π-π interactions between these perimidine segments dominate in the solid product.

Electrically-responsive antimicrobial coatings based on a tetracycline-loaded poly(3,4-ethylenedioxythiophene) matrix.

The growth of bacteria and the formation of complex bacterial structures on biomedical devices is a major challenge in modern medicine. The aim of this study was to develop a biocompatible, conducting and antibacterial polymer coating applicable in biomedical engineering. Since conjugated polymers have recently aroused strong interest as controlled delivery systems for biologically active compounds, we decided to employ a poly(3,4-ethylenedioxythiophene) (PEDOT) matrix to immobilize a powerful, first-line antibiotic: tetracycline (Tc). Drug immobilization was carried out simultaneously with the electrochemical polymerization process, allowing to obtain a polymer coating with good electrochemical behaviour (charge storage capacity of 19.15 ± 6.09 mC/cm2) and high drug loading capacity (194.7 ± 56.2 µg/cm2). Biological activity of PEDOT/Tc matrix was compared with PEDOT matrix and a bare Pt surface against a model Gram-negative bacteria strain of Escherichia coli with the use of LIVE/DEAD assay and SEM microscopy. Finally, PEDOT/Tc was shown to serve as a robust electroactive coating exhibiting antibacterial activity.