Anthracene Moieties Research Articles

Synthesis, In silico Molecular Docking Studies and antimicrobial evaluation of Some New Anthracene Derivatives Tagged with Arylidene, Pyridine, Oxazole, and Chromene Moieties as Promising Inhibitors of Bacterial DNA gyrase

Here, A series of unprecedented derivatives of several heterocyclic compounds, including arylidene, pyridine, oxazole, and chromene, were designed with the anthracene moiety starting from 2-cyano-pyrroloanthracen acetamide (1). The chemical composition of all synthesized compounds was established by spectral analysis FT-IR, 1H-NMR, 13C-NMR, and Mass spectra. Also, the new compounds were docked to the active site of the DNA gyrase B chain enzyme, and the suitable binding interactions were displayed according to their bond lengths and conformational energies. The structure-activity relationship analysis showed that the antimicrobial activity could be modulated by the existence of anthracene moiety, electron-withdrawing groups, and amide linkage. In silico ADMET (absorption, metabolic, distribution, toxicity, and excretion) predictions for the compounds 1-7 were calculated to gain insight into their pharmacokinetics, safety, and drug-likeness profile. The antimicrobial investigations of all synthesized molecules were achieved against Gram-negative (Escherichia coli) and Gram-positive (Bacillus cereus) bacterial strains. Results indicated that the compounds exhibited promising activity against strains. Therefore, the newly hybrid anthracene molecules could serve as promising chemical scaffolds to develop upcoming drug candidates as antimicrobial agents.

Photocontrollable Magnetism and Photoluminescence in a Binuclear Dysprosium Anthracene Complex.

By incorporating photoreactive anthracene moieties into binuclear Dy2O2 motifs, we obtain two new compounds with the formulas [Dy2(SCN)4(L)2(dmpma)4] (1) and [Dy2(SCN)4(L)2(dmpma)2(CH3CN)2] (2), where HL is 4-methyl-2,6-dimethoxyphenol and dmpma is dimethylphosphonomethylanthracene. Compound 1 contains face-to-face π-π interacted anthracene groups that meet the Schmidt rule for a [4 + 4] photocycloaddition reaction, while stacking of the anthracene groups in compound 2 does not meet the Schmidt rule. Compound 1 undergoes a reversible single-crystal-to-single-crystal structural transformation upon UV-light irradiation and thermal annealing, forming a one-dimensional coordination polymer of [Dy2(SCN)4(L)2(dmpma)2(dmpma2)]n (1UV). The process is concomitant with changes in the magnetic dynamics and photoluminescent properties. The spin-reversal energy barrier is significantly increased from 1 (55.9 K) to 1UV (116 K), and the emission color is changed from bright yellow for 1 to weak blue for 1UV. This is the first binuclear lanthanide complex that exhibits synergistic photocontrollable magnetic dynamics and photoluminescence. Ab initio calculations are conducted to understand the magnetostructural relationships of compounds 1, 1UV, and 2.

Synthesis and Optical Properties of 1,2,5,10-Tetraphenylanthra[2,3-b]phosphole Derivatives.

1,2,5,10-Tetraphenylanthra[2,3-b]phosphole oxides and 1-methyl-1,2,5,10-tetraphenylanthra[2,3-b]phospholium salts were prepared, and their optical properties were investigated. The substituent at the para position and the fused anthracene moiety were found to exert significant impacts on the fluorescence properties of the P-bridged 2-styrylanthracene skeleton.

An Overlooked Charge‐Transfer Interaction in the Interfacial Triplet–Triplet Upconversion Process in Blue Organic Light‐Emitting Diodes

AbstractTwo low‐energy triplets can generate one singlet via triplet–triplet upconversion (TTU), and result in an exciton production yield exceeding 25% in conventional fluorescence‐based organic light‐emitting diodes (OLEDs). In most cases, since such low‐energy triplets induce no serious OLED degradation, TTU‐OLEDs are the only commercialized blue OLEDs so far. Herein, it is clarified that the charge‐transfer (CT) interaction at a hole‐transport/emitter‐layer interface is an overlooked pathway to enhance TTU yield significantly. First, a small energy offset at the interface enables the formation of a high‐energy CT exciton. Second, the lower energy triplet state originated from an anthracene moiety in the emitter layer collects the interfacial triplet CT. Third, due to the high‐density interfacial triplets formation, TTU at the interface contributes to the electroluminescence from the emitter layer or blue dopants even at low current density. This finding underlines the important role of the CT interface to exploit the full potential of TTU in pure‐blue OLEDs.

Taming phosphorus mononitride.

Phosphorus mononitride (PN) only has a fleeting existence on Earth, and molecular precursors for the release of this molecule under mild conditions in solution have remained elusive. Here we report the synthesis of an anthracene-based precursor-an anthracene moiety featuring an azidophosphine bridge across its central ring-that dissociates into dinitrogen, anthracene and P≡N in solution with a first-order half-life of roughly 30 min at room temperature. Heated under reduced pressure, this azidophosphine-anthracene precursor decomposes in an explosive fashion at around 42 °C, as demonstrated in a molecular-beam mass spectrometry study. The precursor is also shown to serve as a PN transfer reagent in the synthesis of an Fe-NP coordination complex, through ligand exchange with its Fe-N2 counterpart. The terminal N-bonded complex was found to be energetically preferred, compared to its P-bonded linkage isomer, owing to a significant covalent Fe-pnictogen bond character and an associated less unfavourable Pauli repulsion in the metal-ligand interaction.

Synthesis of Twisted Anthracenes: Induction of Twist Chirality by the Planar Chiral [2.2]Paracyclophane.

Planar chiral [2.2]paracyclophane was employed as chiral scaffolds to twist an anthracene ring by tethering at its 1- and 8-positions; thus, twist chirality was induced in the anthracene moiety. The chiroptical properties of the resulting molecule, including circular dichroism (CD) and circularly polarized luminescence (CPL), were found to be derived from the twist chirality. An analogous molecule bearing long alkyl chains was a viscous liquid at ambient temperature, and its liquid film exhibited good CD and CPL profiles. Theoretical studies are carried out to determine the origin of these properties in the ground and excited states, which reproduced well the experimental results.

Photo-Controlled [4+4] Cycloaddition of Anthryl-Polymer Systems: A Versatile Approach to Fabricate Functional Materials.

The reversible photo-induced [4+4] cycloaddition reaction of anthracene enables multiple cycles of dimerization and scission, allowing phototunable linkage of molecular fragments for the synthesis of polymer scaffolds. New functional materials ranging from hydrogels to shape-memory polymers were designed from anthryl-polymer systems because of their diverse photochemical reactivity and responsiveness. Light as an external stimulus allows for the remote and precise spatiotemporal control of materials without the need for additional reagents. Depending on how the photoreactive anthracene moieties were introduced, the interaction of anthryl-polymer systems with light results in various processes such as polymerization, cyclization, and cross-linking. Structural modifications of anthracene derivatives could shift their absorption from the ultraviolet to the visible light region, widening their range of applications including biologically relevant studies. These applications are further diversified and enhanced by the reversibility of the dimerization reaction using light and heat as stimuli. In this review, current developments in the synthesis and photodimerization of anthracene-containing polymers and their emerging applications in the fabrication of new materials are discussed.

Nonlinear Optical Behavior Due to Charge Transfer within Selected Heterocyclic Anthracenyl Chalcones under Continuous Wave Laser Excitation

Three new heterocyclic-chalcone (HC) derivatives consisting of the π-conjugated system attached to anthracene moiety were proposed for nonlinear optical properties and optical limiting application. The NLO behavior is confirmed through obtained χ3 by Z-scan method. The closed aperture z-scan showed the HC possesses a self-defocusing effect with a negative nonlinear refractive index, n 2 ∼ 10−8 cm/W, with a magnitude of real part of the third-order nonlinear optical susceptibilities, Re χ( 3 ) of the order of 10−7 esu. Open Z-scan results showed that the HC samples demonstrate a reverse saturable absorption (RSA), β ∼ 10−4 cm/W, corresponding to large imaginary parts, Im χ( 3 ) in the order of 10−6 esu. Overall, the Z-scan analysis unveils an excellent value of χ3 in order of 10−6 which indicates good nonlinear material under 532 nm continuous wave laser. The optical limiting study reveals that AC exhibit a strong limiting behavior with action beginning from 0.8 KW/cm2, and seems to be promising optical limiting candidates for future optoelectronic applications. Through B3LYP/6-311G++d,p level of theory Density Functional Theory (DFT), Global Reactivity, Natural Bond Orbital (NBO), and Natural Population were calculated and investigated. Delocalization and hyperconjugation interactions, intramolecular charge transfers, and stabilization energies were discovered using NBO and NPA. The comprehensive studies of Hirshfeld surface (HS) and fingerprint plots (FP) calculations were done in order to evaluate the nature of intermolecular interactions in the compounds. The inclusion of a strong donor and the π-conjugated system improved charge transfer, chemical stability, and optoelectronic properties of the anthracene-heterocyclic chalcone derivatives. As a result, the present work realizes the potential of designed derivatives that can be used in NLO applications.

Synthesis and manifold but controllable emission switching of stilbene-appended polyaromatic terpyridine derivatives via aggregation and trans–cis isomerization

We designed in this work a new series of stilbene-appended terpyridine systems covalently coupled with anthracene, naphthalene and pyrene moieties which can exhibit multiple yet controllable photo-switching behaviors under divergent conditions. Upon aggregation, these emissive compounds display either remarkable blue-shifted emission enhancement or emission quenching with red-shift, depending upon the nature of solvent. Both free- as well as aggregated forms of the compounds undergo trans → cis isomerization upon treating with visible light, accompanied with significant alteration in their spectral behaviors. The reverse cis → trans process is achieved on keeping the photolyzed solutions in dark. Hence, ‘on-off’ and ‘off-on’ emission switching is feasible upon successive exposure to light and keeping in dark. A gradual decrease in rate constant and quantum yield of photoisomerisation was observed with increase in extent of aggregation. Additionally, DFT and TD-DFT calculations are also carried out to interpret experimental spectral bands of the compounds.

Dynamic rotaxane-branched dendrimers with precisely arranged luminogens for efficient light harvesting

Although the development of artificial light-harvesting systems (LHSs) has attracted increasing attention, the construction of novel artificial LHSs with co-existed various types of precisely arranged luminogens has been still a major challenge. Herein, starting from [2]rotaxane building blocks AN-R or TPE-R functionalized with either anthracene or tetraphenylethene (TPE) moiety, a family of novel rotaxane-branched dendrimers containing two types of energy donors on the branches and one pyrene moiety at the central core as energy acceptor have been successfully constructed through a facile, efficient, and controllable divergent approach. Notably, attributed to the solvent-induced switching feature of the rotaxane branches, the integrated rotaxane-branched dendrimers displayed an interesting dynamic feature. More importantly, as revealed by fluorescence spectra, the resultant rotaxane-branched dendrimers displayed enhanced antenna effects along with the increase of dendrimer generation. Therefore, these rotaxane-branched dendrimers described herein could serve as not only promising platforms for light harvesting but also excellent candidates for the construction of smart supramolecular materials for practical applications.

Syntheses of Anthracene-Centered Large PAH Diimides and Conjugated Polymers.

Polycyclic aromatic hydrocarbon (PAH) structures with suitable electron-withdrawing groups are useful building blocks for developing optical and electron-transporting materials. Here, we report the application of a double benzannulation process to the syntheses of PAH diimides with enlarged π-frameworks featuring a central anthracene moiety. The preparations are realized by copper-catalyzed [4+2] cycloaddition of ethynyl-substituted aromatic dicarboximide to 2,5-bis(phenylethynyl)terephthalaldehyde, followed by intramolecular photocyclization or direct arylation via Heck cross coupling. A central symmetric benzo[1,2-k:4,5-k']-bis(fluoranthene)-3,4,12,13-tetracarboxyl diimide (BFDI) is acquired, with the single crystal structure revealing its completely planar polycyclic skeleton. Such a shape-persistent PAH expectedly exhibits a tendency to stack face-to-face and forms J-aggregates. Moreover, BFDI can be difunctionalized site-selectively at the reactive 9 and 10 positions of the anthracene unit and then applied to prepare conjugated polymers. When coupled with 1,4-diketopyrrolo[3,4-c]-pyrrole (DPP) via thiophene and dithiophene linkers, two polymers with significantly broadened absorption bands extended to the near-infrared regime are obtained, evidencing the effective π-conjugative extension ability of BFDI unit.

Ultrastable Covalent Triazine Organic Framework Based on Anthracene Moiety as Platform for High-Performance Carbon Dioxide Adsorption and Supercapacitors.

Conductive and porous nitrogen-rich materials have great potential as supercapacitor electrode materials. The exceptional efficiency of such compounds, however, is dependent on their larger surface area and the level of nitrogen doping. To address these issues, we synthesized a porous covalent triazine framework (An-CTFs) based on 9,10-dicyanoanthracene (An-CN) units through an ionothermal reaction in the presence of different molar ratios of molten zinc chloride (ZnCl2) at 400 and 500 °C, yielding An-CTF-10-400, An-CTF-20-400, An-CTF-10-500, and An-CTF-20-500 microporous materials. According to N2 adsorption–desorption analyses (BET), these An-CTFs produced exceptionally high specific surface areas ranging from 406–751 m2·g−1. Furthermore, An-CTF-10-500 had a capacitance of 589 F·g−1, remarkable cycle stability up to 5000 cycles, up to 95% capacity retention, and strong CO2 adsorption capacity up to 5.65 mmol·g−1 at 273 K. As a result, our An-CTFs are a good alternative for both electrochemical energy storage and CO2 uptake.

Synthesis and electrical properties of new blue emitter having boron atom and anthracene moiety

Boron-based blue light-emitting materials, 3,11-bis(10-phenylanthracen-9-yl)-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene [PA-DOBNA] was prepared with the composition of DOBNA core moiety and 9-phenylanthracene (PA) moiety as side group. The synthesized material showed excellent thermal stability with a high Td of > 400 °C. The doped device using dopant exhibited current efficiency (CE) of 2.90 cd/A and EQE of 4.40% at a current density of 10 mA/cm2. Commission Internationale de L’Eclairage (CIE) coordinates for non-doped and doped devices are (0.16, 0.18) and (0.15, 0.06) corresponding to the EL peaks at 457 and 446 nm, respectively. In addition, the doped device data showed a deep-blue emission of CIE (x = 1.15, y = 0.06) suitable for UHD-TV.

Reversible [4 + 2] Photooxygenation in Anion-Coordination-Driven-Assembled A2L2-Type Complexes.

Two bis-bis(urea) ligands (L1 and L2) incorporating the photoactive 9,10-diphenylanthracene fragment were designed for the construction of anion-coordination-driven assemblies and subsequent oxygenation of anthracene moieties for singlet oxygen storage. The corresponding A2L2-type sulfate complexes [TEA]4[(SO4)2(L1)2] (1) and [TEA]4[(SO4)2(L2)2] (2), where TEA = tetraethylammonium, were achieved by coordinating the ligands L1 or L2 with sulfate anions. Both 1 and 2 were able to undergo [4 + 2] photooxygenation to form endoperoxide photoproducts 1-EPO and 2-EPO, which can be partially converted back to the original anthracene compounds after heating. The structures of 1-EPO and 2-EPO were unambiguously confirmed by X-ray crystallography, NMR and UV-vis spectroscopy, and high-resolution electrospray ionization mass spectrometry.

1,2,3-Tri(9-anthryl)benzene: Photophysical Properties and Solid-State Intermolecular Interactions of Radially Arranged, Congested Aromatic π-Planes.

We report the Negishi coupling based synthesis of 1,2,3-tri(9-anthryl)benzene derivatives containing three radially arranged anthracenes in a π-cluster. In the crystalline state of the unsubstituted derivative, intermolecular π-π and CH-π interactions between the anthracene units drive the formation of the two-dimensional packing structure. Owing to though-space π-conjugation between anthracene units, the substances have unique electronic properties. The excited-state dynamic behavior occurring between the three anthracene moieties, such as exciton localization/delocalization, was elucidated by means of transient absorption measurements and quantum chemical calculations. Interestingly, even though the three anthracenes are closely oriented with approximately 3.0 Å between their C-9 positions, exciton localization on two anthracene units is energetically favorable because of the flexible nature of the radially arranged aromatic rings.

Distance‐Based Structure Characterization of PAMAM‐Related Dendrimers Nanoparticle

Dendrimers are well‐defined nanoparticles, which have far‐reaching application in the field of chemistry. Many efforts have been devoted to development of dendrimer due to thier unique structure and various properties and broad application. It helps in varieties of purposes as a catalyst in drug delivery and drug design. The topological descriptor analyze the structure–property relationship of chemical compounds. In this paper, some numerical expressions have been obtained to understand the behavioral pattern of chiral polyamidoamine (PAMAM) dendrimer and PAMAM anthracene moieties dendrimer. The analytical expression has been plotted and compared with varieties of indices to show how it varies between each indices.

Investigating the photosensitivity of koneramines for cell imaging and therapeutic applications.

The photophysical properties of the anthracene appended koneramines (LAn) were analyzed and utilized as a chemosensor for the selective detection of Cd2+ and Zn2+. The complexation-induced inhibition of PET (photo-induced electron transfer) from the chelating nitrogen atoms to the excited state of the anthracene moiety resulted in a fluorescence "turn-on" signal upon binding with Cd2+ and Zn2+. The confocal microscopic imaging studies performed on the MCF-7 cells validated that the compound is potentially useful for detecting Cd2+ and Zn2+ inside the cells. The cadmium complex exhibited unique bactericidal activity against clinically relevant human pathogens. The excellent activity against multidrug-resistant S. aureus makes the complex useful as a new, easily synthesizable antibiotic. The cadmium complex LAnCdCl2 was not cytotoxic against vero cells with a selectivity index of 40, exhibited concentration dependent bactericidal killing, was non-interactive with several other clinically approved standard drugs, exhibited prolonged post-antibiotic effect (PAE) against S. aureus ATCC 29213 and possesses antibiofilm activity.

Anthracene modified graphene for C60/C70 fullerenes capture and construction of energy storage materials

Graphene functionalized with dianthracene malonate was synthesized and used subsequently for construction of covalently bound graphene-fullerene hybrid nanomaterials. For this purpose, novel approach of Diels–Alder reaction of C60/C70 fullerene cores with anthracene moieties previously introduced onto graphene surface was successfully employed. Structure and composition of obtained graphene and its derivatives were characterized using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopy. Obtained results revealed that both C60 and C70 fullerenes were found to be capable of formation desired Diels–Alder adducts, yielding products of different morphology. Capacitive properties of the synthesized energy storage nanomaterials were determined by means of cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) measurements, revealing that functionalization of graphene with C60 moieties enhances its energy storage properties.

Synthesis and optical properties of a fluorene-benzothiadiazole anthracene copolymer

A novel green-emitting terpolymer of Poly[2,7-(9,9-dihexylfluorene)-co-4,7-(2,1,3-benzothiadiazole)-co-9,10-(anthracene)] (PFABT), containing 9,9-dihexylfluorene and anthracene as electron-pushing unit and benzothiadiazole as electron-pulling unit, was synthesized via Suzuki coupling reaction. Poly[2,7-(9,9-dihexylfluorene)-co-9,10-(anthracene)] (PFA) and Poly[2,7-(9,9-dihexylfluorene)-co-4,7-(2,1,3-benzothiadiazole)] (PFBT) copolymers were also synthesized for comparative purposes. These copolymers were characterized by GPC, FTIR and 13C NMR and computational calculations were performed using density functional theory (DFT) and its time-dependent version (TDDFT) at CAM-B3LYP/6–311 +G(d,p) level. Natural transition orbitals (NTO) and vertical excitation energies were obtained from oligomer models that represent the PFA, PFBT and PFABT polymers. The NTO densities showed that the excitation of the anthracene moiety is responsible for the S1 state on both PFA and PFABT, and that the S2 state of PFBT and PFABT is a consequence of the excitation of the benzothiadiazole-anthracene moiety. We also studied polymer light-emitting diodes (PLEDs) of blends of poly(9-vinylcarbazole) (PVK) as a host matrix with PFA, PFBT or PFABT as guests. The concentrations of the copolymers in the PVK were varied at 5, 25 and 50 wt%. The PL spectra for all blends exhibited one band at 400 nm attributed to PVK and another centered at 535 nm assigned to the PFO derivatives emission. We observed an increase in energy transfer efficiency, E < FRET> , with an increase in the weight ratio of the copolymer (PFA, PFBT or PFABT) into the PVK matrix. All the PLEDs emitted a greenish color, and the concentration of the polymer guest impacted on the performance of the diode.

Synthesis, characterization and DFT study of new anthracene-based semiconducting polyethers for OLED application

New soluble semiconducting anthracene-based polyethers (An-BPS and An-TDP) were synthetized via the Williamson polycondensation of 9,10-dichloromethylanthracene with 4,4′-thiodiphenol (TDP) and bisphenol S (BPS), respectively. The polymers were investigated by density functional theory (DFT): the structural and optoelectronic properties, frontier molecular orbitals (HOMO/LUMO), as well as the infrared, absorption and fluorescence spectra were discussed. The polyethers structures were confirmed by NMR and FTIR spectroscopies, revealing good agreements between experimental and theoretical results. Quasi-identical absorption and blue emission properties were obtained for both polymers in dilute solutions, with a higher fluorescence efficiency for An-BPS. The cyclic voltammetry analysis of these electrochemically active materials showed a higher electron affinity for An-BPS and a lower ionization potential for An-TDP. The DFT calculations showed that the HOMO/LUMO frontier energy distributions are confined on the anthracene moiety in An-BPS. However in An-TDP, the LUMO distribution is localized on anthracene group, while the HOMO is on the TDP unit. The electric behavior of organic light-emitting diodes (OLEDs) based on these macromolecular structures has been investigated via numerical simulation using Silvaco TECAD software. Good electrical properties are estimated, with a low turn on voltages of 3.1 V and 2.9 V for An-TDP and An-BPS, respectively. However, An-BPS showed improved current conductivity, which makes it a good candidate for OLEDs.