Synthesis of imine-derived triazines with Donor–Acceptor properties

Corrochano, Diego R.; Hoz, Antonio de la; Sánchez-Migallón, Ana; Caballero, Rubén; Ramírez, José Ramón

doi:10.1016/j.jclepro.2016.01.053

Cited by 10 publications

(5 citation statements)

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“…The study of organic semiconductor compounds with photochromic properties is of great significance [ 1 ] in the manufacture of devices such as antireflective systems for screens [ 2 ], optical memory systems [ 3 ], optical switches [ 4 , 5 , 6 ], OFETs (Organic Field Effect Transistor) [ 7 , 8 ], smart windows [ 9 ] and a wide variety of sensors [ 10 , 11 , 12 ]. It has been shown that the photochromic response of organic materials depends on the functional groups type and on the molecule structure [ 1 , 13 , 14 , 15 , 16 ]. In previous studies, we reported on the reversible photochromic effect of imine-type materials, and we also reported on the type of terminal functional groups, as well as the synthesis method influencing these properties.…”

Section: Introductionmentioning

confidence: 99%

“…This effect, observed on dyes with fluorene, thiophene, pyrrole and azole heterocycles, has been reported [ 20 , 21 ]. However, the synthesis of these compounds through traditional method [ 13 ] involves solvents, long reaction time and catalysts, generating high production costs. A technique, such as mechanochemistry, that is free from solvents and catalysts and environmentally friendly would make these materials attractive for industrial production.…”

Section: Introductionmentioning

confidence: 99%

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Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies

et al. 2019

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In this work, two oligophenyleneimines type pentamers with terminal aldehydes, designated as DAFCHO (4,4′-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis(azanyl ylidene))bis(9H-fluorene-7,2-diyl))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) and FDACHO (4,4′-((((((2,5-bis(octyloxy)-1,4-phenylene)bis(methanylylidene))bis (azanylylidene))bis(4,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(2,5-bis(octyloxy) benzaldehyde)) were synthesized by mechanochemistry method using 2,5-bis(octyloxy) terephtal aldehyde and 2,7-diaminofluorene or 1,4-phenylenediamine. All compounds were spectroscopically characterized using 1H and 13C-NMR, FT-IR and mass spectrometry MALDITOF. The optical properties of the compounds were analyzed by UV-vis spectroscopy using different solvents. We observed that DAFCHO and FDACHO exhibit interesting photochromic properties when they are dissolved in chloroform and exposed to sunlight for 3, 5 and 10 min. The value of the energy band gap was calculated from the absorption spectra without irradiation Egap(optical). It was 2.50 eV for DAFCHO in chloroform solution, and it decreased to 2.34 eV when it is in films. For FDACHO, it was 2.41 eV in solution and 2.27 eV in film. HOMO (Highest Occupied Molecular Orbital), LUMO (Lowest Unoccupied Molecular Orbital) and Egap(electrochemical) values were obtained by electrochemical studies. The results indicate that the compounds can be considered as organic semiconductors since their values are 2.35 eV for DAFCHO and 2.06 eV for FDACHO. The structural and electronic properties of the compounds were corroborated with a DFT (Density Functional Theory) study.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies

et al. 2019

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Section: Resultsmentioning

confidence: 99%

“…The compounds described in this study lack the extended conjugation required for semiconductor or OLED properties; however, substitution of triazines with thiophene units has been shown to produce semiconductor behavior. 28 This approach could be used to produce disubstituted chlorotriazines that would be expected to pack in a similar way to a surface as C4−C6 and to spin-coat them onto semiconductor substrates relevant for device applications. Preliminary work suggests that bilayers of C6 adhere to the mica and, if proven to be stable under aqueous conditions, these atomically flat surfaces may be a useful alternative to HOPG as a hydrophobic substrate for AFM imaging of adsorbed biomolecules.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthetic Bilayers on Mica from Self-Assembly of Hydrogen-Bonded Triazines

et al. 2020

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This study describes organic thin films prepared under a range of conditions from a model series of bis-N-alkyl chloro-triazines functionalized with short alkyl chains from ethyl to hexyl. The pure films were characterized using atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). When cast on mica, these compounds assemble as crystalline sheets made up of a synthetic bilayer along the crystallographic ab-plane with an internal hydrogen-bonded domain between external alkyl chains. These micron-scale surfaces stack along the c-axis, and increasing the alkyl chain length results in changes to the crystal morphology from needles to nanoscale plates. Thicker films produce nanoscale, pyramidal stacks of bilayers. Compared to atomically flat mica, a rougher, unetched silicon substrate produced irregular domains in the secondary bilayer. Films of mixtures comprising the ethyl derivative with butyl, pentyl, or hexyl derivative were imaged using time-offlight secondary-ion mass spectrometry (ToF-SIMS) that indicated a trend toward a constant stoichiometry with increasing alkyl chain length. AFM of mixed films on mica showed single bilayers of height <2 nm, with an acceptable correlation to the XRD measurements, supporting a constant stoichiometry. These materials permit easy modification of mica to a micron-scale, atomically flat hydrophobic surface, and the use of mixtures with different alkyl chain lengths suggests a method to improve the quality of functional organic thin films.

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“…Donor–acceptor (D–A) conjugated molecules containing alternate electronic donor (D) and acceptor (A) units exhibit tunable optical properties, electronic structures, and redox properties, − which have been extensively investigated and applied in various fields such as organic optoelectronic devices, − sensors , and bioimaging. , With the introduction of this design strategy into synthetic (hetero)cycloarenes, their electronic structure can be controlled by donor and acceptor motifs, while the rigid and well-defined cyclic skeletons remain (Figure a). These D–A (hetero)cycloarenes (DAHCs) are anticipated to combine the bilateral advantages of host–guest properties from macrocycles and interesting electronic properties from the D–A conjugated molecules.…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of Donor–Acceptor Heterocycloarenes Based on Pyrazine Derivatives Possessing Intriguing Iodide Ion Capture Properties

Zhu,

Wang,

et al. 2024

J. Am. Chem. Soc.

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Donor−acceptor (D−A) conjugated systems have been extensively investigated and play important roles in organic electronics. Incorporating D−A structures into (hetero)cycloarenes endows them tunable electronic properties, while the well-defined cavity remains. However, the synthetic complexity of introducing electron-acceptor moieties into (hetero)cycloarenes limits their development and applications. In this paper, the first family of electronically tunable D−A heterocycloarenes (DAHCn, n = 1−5) based on pyrazine derivatives was facilely synthesized through cyclocondensation reaction from a tetraketone-functionalized heterocycloarene precursor prepared using the ketal-protection strategy. The effect of expanded conjugation and the inserted electron-withdrawing group on the electronic structures of the D−A heterocycloarenes was studied systematically by X-ray crystallographic analysis, various spectroscopic measurements, and theoretical calculations. Interestingly, the presence of an electronwithdrawing group polarizes the inner C(sp 2 )−H and significantly increases the binding affinities of D−A heterocycloarenes to the iodide anion. Meanwhile, the anion affinity can be further modulated by the type of attached substituents and the distance of polarization. More importantly, the dicyanopyrazine derivative DAHC3 shows the highest binding strength to the iodide ion as a 2:1 sandwich complex (log β 2 = 12.3 and ΔG = −69.1 kJ mol −1 ), which is the strongest iodide receptor using C(sp 2 )−H hydrogen bonding interactions reported to date. Our finding provides a new strategy to design and synthesize D−A heterocycloarenes and strong anion receptors.

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Synthesis of imine-derived triazines with Donor–Acceptor properties

Cited by 10 publications

References 33 publications

Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies

Mechanosynthesis of Photochromic Oligophenyleneimines: Optical, Electrochemical and Theoretical Studies

Synthetic Bilayers on Mica from Self-Assembly of Hydrogen-Bonded Triazines

Facile Synthesis of Donor–Acceptor Heterocycloarenes Based on Pyrazine Derivatives Possessing Intriguing Iodide Ion Capture Properties

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