One-Step Synthesis of Methoxylated Phloroglucinol Derivatives Promoted by Niobium Pentachloride: An Experimental and Theoretical Approach

Santos, Willian Henrique dos; Oliveira, Eliezer Fernando; Lavarda, Francisco Carlos; Leonarczyk, Ives A.; Ferreira, Marco A. B.; Silva‐Filho, Luiz Carlos da

doi:10.1055/s-0036-1588730

Cited by 9 publications

(3 citation statements)

References 4 publications

(6 reference statements)

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“…Gaussian 09 34 software package was used to calculate the properties of all molecules designed in this work, and the spin density distribution of base monomers and base pairs was visualized using the Multiwfn software 35 in combination with the VMD program. 36 Because M06-2X has certain advantages in dealing with weak interactions, we chose it (at the unrestricted spin-polarized theory level) with a 6-311++G(d,p) basis set 37 to optimize the geometric structures, analyze the frequencies, and calculate the energies of the CS singlet, openshell broken-symmetry (BS) singlet, and T states.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Theoretical Simulation on Regulating the Magnetic Coupling Properties of Diradical Artificial Bases

et al. 2022

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In this work, we computationally designed a series of diradical molecules with obvious magnetic coupling properties based on newly synthesized artificial bases, 6-amino-3-(1′-β-d-2′-deoxyribofuranosyl)-5-nitro-1H-pyridin-2-one (Z), 2-amino-8-(1′-β-d-2′-deoxyribofuranosyl)-imidazo-[1,2a]-1,3,5-triazin-[8H]-4-one (P), 6-amino-9[(1′-β-d-2′-deoxyribofuranosyl)-4-hydroxy-5-(hydroxymethyl)-oxolan-2-yl]-1H-purin-2-one (B), and found two methods (base pairing and nitro group rotation) of regulating the magnetic magnitude, making them become magnetic switches with promising prospects. On one hand, the modified diradical artificial base P3 possesses an excellent magnetic exchange coupling constant due to its spin density concentration on a unique spin polarization path. Because of the serious mismatch between the singly occupied molecular orbital (SOMO) and the lowest unoccupied molecular orbital (LUMO) of Z-P3 base pairing, the magnetic coupling property of the Z-P3 base pair disappears, which indicates that the base pairing can be used as an effective means to regulate the molecular magnetic coupling properties. On the other hand, the investigation shows that the rotation of the nitro group on Z has an influence on the energy gaps between the closed-shell (CS) singlet and triplet (T) states of the base pairs formed by Z-analogues and thereby the expression of magnetic coupling properties. This work can help to develop the modification strategy of the diradical base and provide theoretical guidance for the design and synthesis of magnetic coupling materials with controllable magnetic coupling properties.

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Section: Theoretical Methodsmentioning

confidence: 99%

Theoretical Simulation on Regulating the Magnetic Coupling Properties of Diradical Artificial Bases

et al. 2022

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“…Calculations were performed on the nitroxide diradical nucleobases to obtain a comprehensive understanding of their structural, electronic, and magnetic spin coupling properties using the Gaussian 09 package. 48 The molecular geometric optimizations, frequency analyses, and energy calculations of the CS singlet, broken symmetry (BS) open-shell singlet, and triplet (T) state of them were performed at the unrestricted spin polarized theory level (M06-2X) with a 6-311++G (d,p) basis set. 49 An expression of the magnetic exchange coupling constant is given as 50…”

Section: ■ Introductionmentioning

confidence: 99%

Rational Design of Magnetic DNA Motifs with Diradical Character: Nitroxide Functionalization of Nucleobases

Zhao

2018

J. Phys. Chem. C

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In the current work, the nitroxide radical groups are utilized to functionalize the nucleobases, obtaining the nucleobase diradical building blocks for magnetic DNA with significant ferromagnetic or antiferromagnetic coupling characteristics. The nitroxide functionalization strategies include introduction of nitroxide radical group to the carbon site and oxidization of the amino group in nucleobases, and the diradical-functionalized nucleobases are denoted by 2NO X, where X = A, G, T, and C bases. The density functional theory calculations reveal that these nitroxide diradicalized nucleobases are stable and have large magnetic spin coupling magnitudes. Almost all of them possess antiferromagnetic-like spin coupling characteristics with considerably large spin coupling constants [J = −671.7 ( 2NO A1), −463.3 ( 2NO A3), −370.5 ( 2NO G), −494.9 ( 2NO C1), −3265.5 ( 2NO T), and −2445.5 cm −1 ( 2NO C3)] expect for 2NO C2 and 2NO A2 which have the ferromagnetic-like spin coupling characteristics (J = 149.1 and 440.7 cm −1 ), respectively. The spin alternation rule works well for these nitroxide-diradicalized nucleobases in interpreting the magnetic spin coupling characters although such heterocyclic nucleobases (purine and pyrimidine) are as the couplers, and the spin coupling constants present good linear relationships with the highest occupied molecular orbital−lowest unoccupied molecular orbital energy gaps and the energy gaps between the closed-shell singlet and triplet state of these nucleobase diradicals. Besides, their magnetic coupling properties are also analyzed by the shape of the singly occupied molecular orbitals (SOMOs) and SOMO−SOMO energy splitting of the triplet state, the H-bonding with their complementary nucleobases, and the nitroxide radical group orientations. Clearly, this work provides a novel strategy for the rational design of the magnetic DNA motifs with well-defined diradical characters and also provides insights into the spin coupling interactions in these nucleobasebased magnet building blocks of the magnetic DNA nanowires.

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“…However, they are not always cost competitive nor easily scaled up. As part of our research interests on synthetic methodologies using NbCl 5 [40][41][42][43][44][45][46][47][48][49][50], we report a new approach for the functionalization of 4formylphthalonitrile (1) with substituted anilines and terminal phenylacetylenes via a multicomponent reaction (MCR) promoted by NbCl 5 in the presence of p-chloranil.…”

Section: Introductionmentioning

confidence: 99%

Multicomponent reactions mediated by NbCl 5 for the synthesis of phthalonitrile-quinoline dyads: Methodology, scope, mechanistic insights and applications in phthalocyanine synthesis

et al. 2018

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Herein, we demonstrate the efficiency of NbCl 5 to promote a multicomponent reaction (MCR) for the synthesis of a library of phthalonitrile-quinoline dyads, which are very useful and new functionalized building blocks for phthalocyanine (PC) synthesis. Experimental mechanistic insights on the key MCR process are described, using a deuterated reagent, clearly showing the pericyclic nature of a hetero-Diels-Alder reaction. Examples of phthalocyanine (PC) syntheses were performed in order to demonstrate the versatility of the phthalonitrile-quinoline dyads. Preliminary photophysical measurements show that our phthalonitrile library is very promising for the production of new molecular scaffolds of PC derivatives with potential applications.

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One-Step Synthesis of Methoxylated Phloroglucinol Derivatives Promoted by Niobium Pentachloride: An Experimental and Theoretical Approach

Cited by 9 publications

References 4 publications

Theoretical Simulation on Regulating the Magnetic Coupling Properties of Diradical Artificial Bases

Theoretical Simulation on Regulating the Magnetic Coupling Properties of Diradical Artificial Bases

Rational Design of Magnetic DNA Motifs with Diradical Character: Nitroxide Functionalization of Nucleobases

Multicomponent reactions mediated by NbCl 5 for the synthesis of phthalonitrile-quinoline dyads: Methodology, scope, mechanistic insights and applications in phthalocyanine synthesis

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