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New benzo[h]quinolin-10-ol derivatives with one or two 2-cyanoacrylic acid units were synthesized with a good yield in a one-step condensation reaction. Chemical structure and purity were confirmed using NMR spectroscopy and elemental analysis, respectively. The investigation of their thermal, electrochemical and optical properties was carried out based on differential scanning calorimetry, cyclic voltammetry, electronic absorption and photoluminescence measurements. The analysis of the optical, electrochemical and properties was supported by density functional theory studies. The synthesized molecules were applied in dye-sensitized solar cells as sensitizers and co-sensitizers with commercial N719. The thickness and surface morphology of prepared photoanodes was studied using optical, scanning electron and atomic force microscopes. Due to the utilization of benzo[h]quinolin-10-ol derivatives as co-sensitizers, the better photovoltaic performance of fabricated devices compared to a reference cell based on a neat N719 was demonstrated. Additionally, the effect of co-adsorbent chemical structure (cholic acid, deoxycholic acid and chenodeoxycholic acid) on DSSC efficiency was explained based on the density functional theory.
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PAHs (polycyclic aromatics hydrocarbons), the compound group that contains perylene and its derivatives, including functionalized ones, have attracted a great deal of interest in many fields of science and modern technology. This review presents all of the research devoted to modifications of PAHs that are realized via the Diels-Alder (DA) cycloaddition of various dienophiles to the bay regions of PAHs, leading to the π-extension of the starting molecule. This type of annulative π-extension (APEX) strategy has emerged as a powerful and efficient synthetic method for the construction of polycyclic aromatic hydrocarbons and their functionalized derivatives, nanographenes, and π-extended fused heteroarenes. Then, [4 + 2] cycloadditions of ethylenic dienophiles, -N=N-, i.e., diazo-dienophiles and acetylenic dienophiles, are presented. This subject is discussed from the organic synthesis point of view but supported by theoretical calculations. The possible applications of DA cycloaddition to PAH bay regions in various science and technology areas, and the prospects for the development of this synthetic method, are also discussed.
Assuntos
Reação de Cicloadição , Perileno/química , Hidrocarbonetos Policíclicos Aromáticos/química , Ésteres/química , TermodinâmicaRESUMO
New D-π-D-π-A low-molecular-weight compounds, based on a phenothiazine scaffold linked via an acetylene unit with various donor moiety and cyanoacrylic acid anchoring groups, respectively, were successfully synthesized. The prepared phenothiazine dyes were entirely characterized using nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The compounds were designed to study the relationship between end-capping donor groups' structure on their optoelectronic and thermal properties as well as the dye-sensitized solar cells' performance. The effect of π-conjugation enlargement by incorporation of different heterocyclic substituents possessing various electron-donor affinities was systematically experimentally and theoretically examined. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were implemented to determine the electronic properties of the novel molecules.
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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.
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Series of Re(I) carbonyls complexes were designed and synthesized to explore the impact of the triimine skeleton and number of methoxy groups attached to aryl substituents on their optoelectronic and thermal properties. The chemical structures of the prepared complexes were confirmed by 1H and 13C NMR spectroscopy, HR-MS, elemental anlsysis, and X-ray measurements. DSC measuremtns showed that they melted in the range of 198-325⯰C. Some of them form stable molecular glasses with high glass transition temperatures (158-173⯰C). Experimentally obtained optical properties were supported by DFT calculations. The UV-Vis spectra display a series of overlapping absorption bands in the range 200-350â¯nm, and much weaker broad band in the visible spectral region, due to intraligand and charge transfer transitions, respectively. All synthesized complexes were emissive in solution and in solid state as powder. Moreover, when applied in diodes, some of them exhibited ability for emission of light under external voltage with maximum of electroluminescence band located at 591-630â¯nm.
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Five novel derivatives of pyrene, substituted at positions 1,3,6,8 with 4-(2,2-dimethylpropyloxy)pyridine (P1), 4-decyloxypyridine (P2), 4-pentylpyridine (P3), 1-decyl-1,2,3-triazole (P4), and 1-benzyl-1,2,3-triazole (P5), are obtained through a Suzuki-Miyaura cross-coupling reaction or CuI -catalyzed 1,3-dipolar cycloaddition reaction, respectively, and characterized thoroughly. TGA measurements reveal the high thermal stability of the compounds. Pyrene derivatives P1-P5 all show photoluminescence (PL) quantum yields (Φ) of approximately 75 % in solution. Solid-state photo- and electroluminescence characteristics of selected compounds as organic light-emitting diodes are tested. In the guest-host configuration, two matrixes, that is, poly(N-vinylcarbazole) (PVK) and a binary matrix consisting of PVK and 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD) (50:50â wt %), are applied. The diodes show red, green, or blue electroluminescence, depending on both the compound chemical structure and the actual device architecture. In addition, theoretical studies (DFT and TD-DFT) provide a deeper understanding of the experimental results.
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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.