Simple Donor-π-Acceptor Compounds Exhibiting Aggregation-Induced Emission as Hidden Fingerprints Detecting Agents.

Latent fingerprints are a significant carrier of information for a court expert. To detect this type of forensic trace, what is necessary is a method that is easy to use, compact, and versatile. The research aimed to investigate the physicochemical properties of luminescent substances of donor-π-acceptor systems in terms of their potential use in detecting hidden fingerprints. During the research, a group of fluorene compounds consisting of the (-CH=C(CN)(COOR)) moiety was designed and successfully synthesized. The optical, electrochemical, and aggregation-induced emission properties were studied. The aggregation-induced emission of compounds has been studied in the mixture of THF (as a good solvent) and water (as a poor solvent) with different water fractions ranging from 0% to 99%. Due to the molecular structure, substances showed different affinities to organic traces. As a result, it was noticed that all compounds showed the AIE phenomenon, while during tests on latent fingerprints, it was observed that two substances had particularly forward-looking features in this field.

Electroactive Dyes Based on 1,8-Naphthalimide with Acetylene Linkers as Promising OLED Materials - the Relationship Between Structure and Photophysical Properties.

Four A-π-D-π-A type small organic molecules with 1,8-naphthalimide motifs were successfully synthesised. The designed compounds are built of two 1,8-naphthalimide units linked via ethynyl π-linkages with selected functionalised donor motifs i. e. 2,2'-bithiophene, fluorene, phenothiazine and carbazole derivative. The synthesis based on Sonogashira cross-coupling allowed us to obtain the presented dyes with good yields. The resulting symmetrical small molecules' optical, electrochemical and thermal properties were thoroughly investigated, and their potential applicability for the OLED devices was demonstrated. In addition, the relationship between molecular structure and properties was considered by employing experimental and theoretical studies. As a result of using various donor groups, it was possible to achieve efficient electroluminescence in the range from green (DEV4) to orange-red light (DEV3) with a maximum luminance of 3 820 cd/m2 for DEV4. Upon the insertion of an acetylene linker to the designed molecules, the free rotation of D and A fragments, and hence the effective π-electron communication within the entire molecule, is possible, which was confirmed by DFT studies. The obtained dyes are characterised by high thermal stability, reversible oxidation-reduction process, satisfactory optoelectronic properties and good solubility in organic solvents, which is advisable for the application in small molecular organic light-emitting diodes (SM-OLEDs) technology.

The Role of Intermolecular Interaction on Aggregation-Induced Emission Phenomenon and OLED Performance.

In this work, the role of intermolecular interaction on the aggregation-induced emission (AIE) phenomenon and organic light-emitting diodes' (OLEDs) performance was investigated. During the research, a group of compounds consisting of the (-CH=C(CN)(COOR)) moiety with identical energy parameters was designed using the DFT approach and successfully synthesized. The optical, electrochemical, and aggregation-induced emission properties were studied. The aggregation-induced emission of compounds has been studied in the mixture of MeCN (as a good solvent) and water (as a poor solvent) with different water fractions ranging from 0% to 99%. Moreover, the time dependence on the AIE feature was also evaluated. Thanks to their molecular structures, almost identical behavior of these substances in dilute solutions was observed. For molecules that exhibit the strong AIE phenomenon, emission efficiency increases rapidly during aggregation. What is also very interesting is it has been shown that by introducing an appropriate substituent, one can control the degree of intermolecular interactions and "control" the length of the emitted wave. Finally, OLEDs were fabricated by the spin-coating/evaporation hybrid method. Devices showed green-blueish electroluminescence (CIE coordinates: 0.107, 0.165) with maximum luminance reaching 25 cd m-2 and EQE reaching 2%.

APEX Strategy Represented by Diels-Alder Cycloadditions-New Opportunities for the Syntheses of Functionalised PAHs.

Diels-Alder cycloaddition of various dienophiles to the bay region of polycyclic aromatic hydrocarbons (PAHs) is a particularly effective and useful tool for the modification of the structure of PAHs and thereby their final properties. The Diels-Alder cycloaddition belongs to the single-step annulative π-extension (APEX) reactions and represents the maximum in synthetic efficiency for the constructions of π-extended PAHs including functionalised ones, nanographenes, and π-extended fused heteroarenes. Herein we report new applications of the APEX strategy for the synthesis of derivatives of 1,2-diarylbenzo[ghi]perylene, 1,2-diarylbenzo[ghi]perylenebisimide and 1,2-disubstituted-benzo[j]coronene. Namely, the so far unknown cycloaddition of 1,2-diarylacetylenes into the perylene and perylenebisimide bay regions was used. 1,2-Disubstituted-benzo[j]coronenes were obtained via cycloaddition of benzyne into 1,2-diarylbenzo[ghi]perylenes by using a new highly effective system for benzyne generation and/or high pressure conditions. Moreover, we report an unprecedented Diels-Alder cycloaddition-cycloaromatisation domino-type reaction between 1,4-(9,9-dialkylfluoren-3-yl)-1,3-butadiynes and perylene. The obtained diaryl-substituted core-extended PAHs were characterised by DFT calculation as well as electrochemical and spectroscopic measurements.

Solvent-free thiophene-based electrolytes: synthesis of new liquid-crystalline ionic conductors for batteries: part I.

New liquid crystalline thiophene esters, thiophene-3-yl 3,4,5-tris(n-dodecan-1-yloxy)benzoate (ThBz1) and thiophene-3-yl 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate (ThBz2), were synthesized for use in lithium-ion batteries as safe, new solvent-free ionic conductors. Both compounds were synthesized in multi-step reactions and were characterized via1H, 13C NMR and FT-IR spectroscopy, confirming the formation of the desired products. ThBz1 and ThBz2 showed good thermal stability and liquid crystalline behaviour. Electrochemical tests demonstrated a wide electrochemical window of 4 V for both tested ThBz compounds. Moreover, preliminary battery tests for new electrolytes in the LiCoO2/Li4Ti5O12 system confirmed their applicability in lithium-ion batteries.

Structural and electrochemical studies of TiO2 complexes with (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivative bases towards organic devices.

Three (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (-HC[double bond, length as m-dash]CH-) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (SAI1 and SAI2) and -5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about -3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO-LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500-1700 cm-1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C[double bond, length as m-dash]N)-TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm-2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes.

Synthesis and characterization of two new TiO2-containing benzothiazole-based imine composites for organic device applications.

The effect of the presence of titanium dioxide in two new imines, (E,E)-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[d][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and (E)-N-[(benzo[d][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol-gel method) exhibited a surface area of 59.5 m2/g according to Brunauer-Emmett-Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett-Joyner-Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m3/g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Colhk). The imine:TiO2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO-LUMO energy levels compared to pure TiO2. This implies that TiO2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO2 surface with SP1 and SP2 were observed. The imine:TiO2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications.

Symmetrical N-acylsubstituted dihydrazones containing bithiophene core--Photophysical, electrochemical and thermal characterization.

Four symmetrical N-acylsubstituted dihydrazones containing bithiophene core were synthesized from condensation of 2,2'-bithiophene-5,5'-dicarboxyaldehyde with benzoic, isonicotinoyl, 2-thiophenic and 2-furoic hydrazide. The obtained compounds were characterized through the data from (1)H nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), elemental analysis, UV-vis absorption spectroscopy, photoluminescence (PL), cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements. Additionally, the electronic properties including orbital energies and resulting energy gaps were calculated by density functional theory (DFT). Their thermal behavior was investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). They were thermal sable up to 320°C. The prepared N-acylsubstituted dihydrazones emitted light with λ(em) in the range of 499-530 nm in solution, whereas, in solid state as blend with PMMA blue emission was observed. They undergo quasi-reversible and irreversible electrochemical reduction and oxidation processes, respectively. Additionally, the selected compounds were tested preliminary as component of active layer in organic photovoltaic cells. The highest value of power conversion efficiency, equal to 1.68% under simulated 100 mW/cm(2) AM 1.5G irradiation was found for device with the architecture ITO/PEDOT:PSS/P3HT:PCBM:FBTH (1:2:2)/Al.

Multifaceted strategy for the synthesis of diverse 2,2'-bithiophene derivatives.

New catalytically or high pressure activated reactions and routes, including coupling, double bond migration in allylic systems, and various types of cycloaddition and dihydroamination have been used for the synthesis of novel bithiophene derivatives. Thanks to the abovementioned reactions and routes combined with non-catalytic ones, new acetylene, butadiyne, isoxazole, 1,2,3-triazole, pyrrole, benzene, and fluoranthene derivatives with one, two or six bithiophenyl moieties have been obtained. Basic sources of crucial substrates which include bithiophene motif for catalytic reactions were 2,2'-bithiophene, gaseous acetylene and 1,3-butadiyne.

(Photo)physical Properties of New Molecular Glasses End-Capped with Thiophene Rings Composed of Diimide and Imine Units.

New symmetrical arylene bisimide derivatives formed by using electron-donating-electron-accepting systems were synthesized. They consist of a phthalic diimide or naphthalenediimide core and imine linkages and are end-capped with thiophene, bithiophene, and (ethylenedioxy)thiophene units. Moreover, polymers were obtained from a new diamine, N,N'-bis(5-aminonaphthalenyl)naphthalene-1,4,5,8-dicarboximide and 2,5-thiophenedicarboxaldehyde or 2,2'-bithiophene-5,5'-dicarboxaldehyde. The prepared azomethine diimides exhibited glass-forming properties. The obtained compounds emitted blue light with the emission maximum at 470 nm. The value of the absorption coefficient was determined as a function of the photon energy using spectroscopic ellipsometry. All compounds are electrochemically active and undergo reversible electrochemical reduction and irreversible oxidation processes as was found in cyclic voltammetry and differential pulse voltammetry (DPV) studies. They exhibited a low electrochemically (DPV) calculated energy band gap (Eg) from 1.14 to 1.70 eV. The highest occupied molecular orbital and lowest unoccupied molecular orbital levels and Eg were additionally calculated theoretically by density functional theory at the B3LYP/6-31G(d,p) level. The photovoltaic properties of two model compounds as the active layer in organic solar cells in the configuration indium tin oxide/poly(3,4-(ethylenedioxy)thiophene):poly(styrenesulfonate)/active layer/Al under an illumination of 1.3 mW/cm2 were studied. The device comprising poly(3-hexylthiophene) with the compound end-capped with bithiophene rings showed the highest value of Voc (above 1 V). The conversion efficiency of the fabricated solar cell was in the range of 0.69-0.90%.