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Antiaromatic porphyrinoids have attracted significant attention owing to their unique electronic properties and potential applications. However, synthesis of antiaromatic contracted porphyrinoids is challenging owing to the inherent instability associated with smaller ring sizes. In this study, we report the synthesis and characterization of the first stable trioxa[16]triphyrin(2.1.1), a novel 16π antiaromatic contracted porphyrinoid. We utilized a core modification approach to stabilize the [16]triphyrin(2.1.1). X-ray crystallographic analysis revealed a nearly planar structure. Electrochemical studies demonstrated reversible oxidation behavior and a small HOMO-LUMO gap, which was consistent with its antiaromatic nature. Chemical oxidation yielded an aromatic [14]triphyrin(2.1.1) dication, highlighting the antiaromaticity-aromaticity switching capability of this system. This synthesis involved the discovery of a key intermediate, dihydrotrioxatriphyrin(2.1.1), which underwent oxidative dehydrogenation to yield the target compound. Theoretical calculations suggested that dihydrotrioxatriphyrin(2.1.1) formed via a rare 16π electrocyclic reaction. The successful synthesis and characterization of this stable trioxa[16]triphyrin(2.1.1) underscores the potential of the core modification strategies for the rational design of novel antiaromatic systems with tunable properties. Moreover, the discovery of the rare 16π electrocyclic reaction advances the understanding of high-order pericyclic processes and may inspire new synthetic strategies for complex macrocyclic compounds.
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Porphyrins are attracting increasing attention in materials science and photochemistry owing to their unique properties and diverse applications. This study focuses on modifying and tuning the absorption properties of porphyrins, specifically those of quinoidal porphyrins, to extend their spectral range into the near-infrared (NIR) region. We report the synthesis and structural and physical properties of quinone compounds derived from doubly and triply linked diporphyrins and their metal complexes. Doubly linked diporphyrinquinone exhibits broad panchromatic absorption properties in solution owing to its low symmetry. Metal complexation markedly extends its absorption range into the near-infrared region. In contrast, the metal complexes of the triply linked diporphyrinquinones exhibit sharp and strong absorption bands in the visible to near-infrared region owing to their higher symmetry. The longest absorption wavelength of the triply linked diporphyrinquinones was approximately 1500â nm, which was significantly more red-shifted than that of the doubly linked ones.
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Facile redox-induced aromatic-antiaromatic interconversions were accomplished by using ß-tetracyano-21,23-dithiaporphyrin (CN4 S2 Por). Introduced cyano groups not only increased the reduction potential of the porphyrin core but also stabilized the antiaromatic isophlorin (CN4 S2 Iph) by π conjugation. The reduction of CN4 S2 Por with hydrazine in polar solvents quantitatively affords CN4 S2 Iph, even under ambient conditions. CN4 S2 Iph retains a nearly planar conformation and exhibits considerable antiaromaticity. Aerobic oxidation of CN4 S2 Iph to CN4 S2 Por occurs in nonpolar solvents. This study was conducted to contribute to the understanding of the structure-antiaromaticity relationship.
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Dinuclear rare-earth (TbIII , YIII ) triple-decker complexes with a fused diporphyrin (FP) and two tetraphenylporphyrin (TPP) ligands were synthesized in neutral, dianionic, and diprotonated forms. The neutral forms have large open shell biradical character, as determined from the temperature dependency of the magnetic susceptibility measurements and theoretical calculations. The coupling value (J=-1.4â kcal mol-1 , -487â cm-1 ) of the radical centers in the neutral form of the YIII complex indicates weak pairing interactions. Theoretical calculations on the neutral form reveal a significant biradical character (y=68 %). Furthermore, the TbIII complex exhibits multi-redox states, having more than eight clear peaks in the voltammetry curves. The optical (3700â nm, 0.33â eV) and electrochemical measurements (3400â nm, 0.36â eV) indicate that the neutral form has very small HOMO-LUMO energy gap. Despite the large biradical character, the neutral complexes are thermally stable and do not decompose on heating at 120 °C. These complexes with unique characteristics are promising candidates for use in molecular electronics, optics, and spintronics.
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A facile and metal-free method for the preparation of free base meso-aminodiarylporphyrins from readily available meso-bromodiarylporphyrins is described. Simple treatment of meso-bromoporphyrins with sodium azide and sodium ascorbate in DMF affords the corresponding meso-aminoporphyrins in very good yields. This method involves the aromatic nucleophilic substitution (SNAr) of a bromo group with an azido group and the subsequent in situ reduction of the introduced azido group by sodium ascorbate. This amination reaction can be scaled up to gram scale without any decrease of the product yield. The amination reaction of free base meso-dibromoporphyrin affords a monoaminated product selectively, whereas that of the Ni(II) complex furnishes a diaminated product that is oxidized by air under ambient conditions but isolable as a trifluoroacetyl ester. Metal-insertion reactions of the obtained free base aminoporphyrins afford the corresponding metal complexes (Ni(II), Cu(II), Zn(II), and Pd(II)) all in good yields except the Pd(II) complex. Synthetic methods for the preparation of N-mono- or dialkylaminoporphyrins from the free base meso-aminoporphyrins have been also established.
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Direct structural evidence of the presence and location of the attached proton in the protonated form of rare earth bis(porphyrinato) double-decker complexes is obtained from an X-ray diffraction study of single crystals for a series of protonated forms of bis(tetraphenylporphyrinato) complexes [M(III)(tpp)(tppH)] (M = Tb, Y, Sm, Nd, and La). When CHCl3 is used as a solvent for crystallization of the complexes, their nondisordered molecular structures are obtained and the attached proton is identified on one of the eight nitrogen atoms. Use of other solvents affords another type of crystal, in which the position of the proton is disordered and thus the molecular structure is averaged. La complex also affords the disordered average structure even when CHCl3 is used for crystallization. A variable-temperature diffraction study for the Tb complex reveals that the dynamics of the proton in the nondisordered crystal is restricted.
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Polyaniline, which is formed by the oxidative polymerization of aniline, is a widely explored conducting polymer with several stable oxidation states, and can be applied in advanced materials, including sensing devices and electrochemical catalysts. The marriage of polyanilines with the diverse chemistry of porphyrins is expected to confer new properties, including a combination of electrical, optical, magnetic and chemical properties. Herein, we demonstrate that meso-aminodiarylporphyrin, a porphyrin analogue of aniline, undergoes oxidative oligomerization in an acidic solution under an oxygen atmosphere to yield stable oligomeric products that are analogous to fully oxidized polyanilines. The so-formed oligomers are composed of the same number of electron-rich porphyrinoid and electron-deficient quinoid moieties, and they exhibit a broad electronic absorption band in the near infrared (NIR) region, which is attributable to intramolecular charge transfer (ICT) transition from electron-rich porphyrinoid moieties to electron-deficient quinoid ones. The quinoid moieties in the oligomers could be reversibly reduced using sodium ascorbate to obtain all-porphyrinoid oligomers that resemble fully reduced polyanilines. The fully reduced oligomers do not exhibit the NIR ICT band. Furthermore, three types of partially reduced tetramers consisting of a single quinoid moiety were also obtained, among which two interconverted in solution. Their interconversion was significantly accelerated in the presence of a protic solvent. This result is consistent with the high electron conductivity of partially oxidized polyanilines following their protonation.
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The singlet-singlet energy transfer rate in a new zinc(II) porphyrin-free base porphyrin dimer, having a m-bis(phenylethynyl)phenylene bridge, was found to be slower than that in the corresponding p-bis(phenylethynyl)phenylene-bridged dimer, despite the shorter donor-acceptor distance and pathway. The slower rate is interpreted as evidence for a major contribution of the superexchange mechanism.
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The magnetic circularly polarized luminescence (MCPL) and photoluminescence (PL) spectra of achiral (2,3,7,8,12,13,17,18-octaethylporphyrinato)platinum(II), PtOEP, and [2-(4',6'-difluorophenyl)pyridinato-N,C2' ]platinum(II) acetylacetonate-O,O, F2 -ppyPt(acac), in toluene and dichloromethane solutions were recorded under an external magnetic field of 1.6â T with N-up and S-up Faraday geometries. The MCPL signs of PtOEP and F2 -ppyPt(acac) were controlled solely by changing the N-up and S-up geometries. The MCPL/PL wavelengths of F2 -ppyPt(acac) in solutions were varied by the ratio of the monomeric and excimeric species.
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Treatment of a meso-diarylporphyrin with PhI(OAc)2 in the presence of BF3 â OEt2 and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso-meso ß-ß doubly-fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000â nm. It has a low HOMO-LUMO gap owing to expanded and low-symmetry π-planes.
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Molecular structures for three oxidation forms (anion, radical, and cation) of terbium(III) bis(porphyrinato) double-decker complexes have been systematically studied. We found that the redox state controls the azimuthal rotation angle (φ) between the two porphyrin macrocycles. For [TbIII (tpp)2 ]n (tpp: tetraphenylporphyrinato, n=-1, 0, and +1), φ decreases at each stage of the oxidation process. The decrease in φ is due to the higher steric repulsion between the phenyl rings on the porphyrin macrocycle and the ß hydrogen atoms on the other porphyrin macrocycle, which results from the shorter interfacial distance between the two porphyrin macrocycles. Conversely, φ=45° for both [TbIII (oep)2 ]-1 and [TbIII (oep)2 ]0 (oep: octaethylporphyrinato), but φ=36° for [TbIII (oep)2 ]+1 . Theoretical calculations suggest that the smaller azimuthal rotation angle of the cation form is due to the electronic interaction in the doubly oxidized ligand system.
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Upon guest recognition, a self-assembled hexa-ruthenium coordination cage shows a chromic shift resulting from the slight conformational change in the panel ligand.
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Field experiments were conducted over 3 years (2012, 2013, and 2015), in which half of the young stage soybean plants were exposed to volatiles from cut goldenrods three times over 2-3 weeks, while the other half remained unexposed. There was a significant reduction in the level of the total leaf damage on exposed soybean plants compared with unexposed ones. In 2015, the proportion of damage to plants by Spodoptera litura larvae, a dominant herbivore, was significantly less in the exposed field plots than in the unexposed plots. Under laboratory conditions, cut goldenrod volatiles induced the direct defenses of soybean plants against S. litura larvae and at least three major compounds, α-pinene, ß-myrcene, and limonene, of cut goldenrod volatiles were involved in the induction. The number of undamaged seeds from the exposed plants was significantly higher than that from unexposed ones. Concentrations of isoflavones in the seeds were significantly higher in seeds from the exposed plants than in those from the unexposed plants. Future research evaluating the utility of weeding volatiles, as a form of plant-plant communications, in pest management programs is necessary.
Assuntos
Glycine max/efeitos dos fármacos , Glycine max/fisiologia , Herbivoria , Isoflavonas/metabolismo , Folhas de Planta/efeitos dos fármacos , Sementes/efeitos dos fármacos , Sementes/metabolismo , Compostos Orgânicos Voláteis/efeitos adversos , Plantas Daninhas/químicaRESUMO
Detection and use of physical noise fluctuations in a signal provides significant advantages in the development of bio- and neuro-sensing and functional mimicking devices. Low-dimensional carbon nanomaterials are a good candidate for use in noise generation due to the high surface sensitivity of these materials, which may themselves serve as the main building blocks of these devices. Here, we demonstrate that the addition of a molecule with high redox activity to a carbon nanotube (CNT) field-effect transistor provides tunable current fluctuation noise. A unique charge-trap state in the vicinity of the CNT surface due to the presence of the single molecule is the origin of the noise, which generates a prominent and unique slow discrete random telegraph signal in the device current. The power spectral density reveals the peculiar frequency limit of the fluctuation for different types of molecules depending on their redox activity and adsorption configuration. These results indicate that the detected noise will provide new opportunities to obtain electronic information for a single molecule combined with a nanotube surface, and that controllability of the noise may contribute to the expansion of noise utilization in future bio-inspired devices.
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An isomer of tetracyanoporphyrinquinodimethane (TCPQ), 5,10-TCPQ, was designed, synthesized, and structurally characterized, and its basic properties were discussed with emphasis on comparison with those of reported 5,15-TCPQ. The title compound was synthesized by a convenient cascade reaction involving a catalyst-free aromatic nucleophilic substitution reaction and the Uno-Takahashi reaction. The obtained π-expanded redox molecule acted as a Wurster-type redox molecule that underwent not only reduction but also oxidation processes. Furthermore, its absorption spectrum showed a large bathochromic shift that extended to the near-IR region, approximately 1150â nm.
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A 'figure-of-eight'-shaped molecule with Pd(ii) at the node was self-assembled into an unprecedented circular tris[2]catenane via reversible double catenation at both loops of the 'figure-of-eight' molecule.
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meso-Mono- or diazidoporphyrins were readily obtained in high yields by the catalyst-free aromatic nucleophilic reaction of the corresponding bromoporphyrins with azide anions under mild conditions. The molecular structures of the obtained azides were unambiguously determined by X-ray crystallographic analysis.
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Azidas/química , Bromo/química , Porfirinas/síntese química , Ânions/química , Catálise , Modelos Moleculares , Estrutura MolecularRESUMO
The constant melting temperature upon the change in the oligonucleotide concentration showed that the oligonucleotide d(CGCTTTGCG) formed a intramolecular hairpin rather than a duplex with an internal loop. We examined the thermodynamic properties of the interaction between the threading intercalator, naphthalene diimides designated as NDI, and a series of hairpin oligonucleotides, d(CGCTnGCG) (n = 3, 4, 5, and 6) designated as CGCn. A complex with a molar ratio of 1:1 was formed between NDI and CGCn. Because the observed negative entropy change was unfavorable for the binding of NDI to CGCn, the binding was driven by the large negative enthalpy change. All of the thermodynamic parameters for the threading intercalation were not significantly changed by the difference in the loop length n. The stem region rather than the loop region of CGCn is mainly involved in the binding of NDI.