Anthracene Derivatives Research Articles

Light-Induced Increase of the Local Molecular Coverage on a Surface.

Light is a versatile tool to remotely activate molecules adsorbed on a surface, for example, to trigger their polymerization. Here, we explore the spatial distribution of light-induced chemical reactions on a Au(111) surface. Specifically, the covalent on-surface polymerization of an anthracene derivative in the submonolayer coverage range is studied. Using scanning tunneling microscopy and X-ray photoemission spectroscopy, we observe a substantial increase of the local molecular coverage with the sample illumination time at the center of the laser spot. We find that the interplay between thermally induced diffusion and the reduced mobility of reaction products steers the accumulation of material. Moreover, the debromination of the adsorbed species never progresses to completion within the experiment time, despite a long irradiation of many hours.

Anthracene and Pyrene Derivatives as Blue Fluorophores: Synthesis, Characterization and Photophysical Properties

Ant hracene and pyrene derivatives have been widely studied as emitting materials in optoelectronic devices due to their excellent fluorescence properties. In the present study, two novel blue fluorophores from anthracene and pyrene (PAP and PTATP) were successfully synthesized using a Suzuki-cross coupling reaction and their photophysical properties were elucidated. PTATP with an extended p-conjugation system had a fluorescence emission maximum in green-blue region at 475 nm, whereas PAP, with a shorter conjugation length, emitted pure-blue emission peak at 442 nm. The study of absorption and emission spectra in various solvents found that both compounds produced solvent-independent spectra due to their non-polar molecules. In addition, the aggregation-caused quenching phenomenon was observed, when the emission spectra were recorded in high water fraction solvent.

Resonant electron capture by polycyclic aromatic hydrocarbon molecules: Effects of aza-substitution.

Resonant electron capture by aza and diaza derivatives of phenanthrene (7,8-benzoquinoline and 1,10-phenanthroline) and anthracene (acridine and phenazine) at incident free electron energies (Ee) in the range of 0-15eV was studied. All compounds except 7,8-benzoquinoline form long-lived molecular ions (M-) at thermal electron energies (Ee ∼ 0eV). Acridine and phenazine also form such ions at epithermal electron energies up to Ee = 1.5-2.5eV. The lifetimes (τa) of M- with respect to electron autodetachment are proportional to the extent of aza-substitution and increase on going from molecules with bent geometry of the fused rings (azaphenanthrenes) to linear isomers (azaanthracenes). These regularities are due to an increase in the adiabatic electron affinities (EAa) of the molecules. The EAa values of the molecules under study were comprehensively assessed based on a comparative analysis of the measured τa values using the Rice-Ramsperger-Kassel-Marcus theory, the electronic structure analysis using the molecular orbital approach, as well as the density functional calculations of the total energy differences between the molecules and anions. The only fragmentation channel of M- ions from the compounds studied is abstraction of hydrogen atoms. When studying [M-H]- ions, electron autodetachment processes were observed, the τa values were measured, and the appearance energies were determined. A comparative analysis of the gas-phase acidity of the molecules and the EAa values of the [M-H]· radicals revealed their proportionality to the EAa values of the parent molecules.

Unveiling All‐Optical Switching Phenomenon in Anthracene Derivatives: A Comprehensive Study on Optical and Nonlinear Optical Multifunctionality

AbstractIn this study, it is considered three anthracene derivatives, characterized meticulously in terms of their chemical structure and product purity. Extensive quantum chemical calculations are conducted to elucidate their optical and nonlinear optical properties, shedding light on the mechanism of photoinduced conformational transformation, a pivotal discovery in this research. Experimental analyses encompassed fundamental optical properties and advanced nonlinear optical phenomena, including z‐scan experiments, second harmonic generation (SHG), and third harmonic generation (THG). Remarkably, a groundbreaking all‐optical switching phenomenon in these materials is experimentally validated, marking a significant advancement and contributing to their potential applications.

Highly efficient hot exciton deep-blue OLEDs based on triphenyl-phosphine oxide modified anthracene derivatives

The utilization of triplet state excitons is important for the efficiency of organic light-emitting diodes (OLEDs). In this work, two isomers (p-PIAnPO and m-PIAnPO) of anthracene-based derivatives with triphenylphosphine oxide (PO) and phenanthroimidazole (PI) in different positions were designed and synthesized. In particular, PO provides large spatial hindrance and promotes hole transport, and PI has excellent bipolar transport ability, which helps to balance carrier transport. The para-linkage (p-PIAnPO) favors conjugation expansion and achieves high luminescence efficiencies, whereas the meta-linkage (m-PIAnPO) provides a highly twisted molecular conformation, thus effectively interrupting conjugation and leading to deep-blue emission. These molecules exhibit excellent thermal stability and efficient electroluminescence properties. Non-doped OLEDs using p-PIAnPO and m-PIAnPO as the light-emitting layers achieve maximum external quantum efficiencies of 6.0% and 4.2% with the λEL at 466 nm and 448 nm, corresponding to high exciton utilization efficiency (EUE) of 59%–88% and 54%–81%. In addition, p-PIAnPO-based OLEDs achieve an ultra-low efficiency roll-off of 1.7% at 1000 cd m−2. Theoretical calculations and experimental results show that the high EUE is mainly attributed to the high-lying reverse intersystem crossing from T3 to S1 namely hot exciton channel.

Photoinduced [2+2] and [4+4] Cycloaddition and Cycloreversion Reactions for the Development of Photocontrollable DNA Binders

AbstractIn the current field of photopharmacology, molecular photoswitches are applied whose interactions with DNA can be triggered or controlled by light. And although several photochromic reactions have been shown to serve this purpose well, the reversible photocycloaddition and photocycloreversion reactions have been largely neglected. This absence of research is surprising because especially the photodimerization of a DNA ligand leads to products with significant change of the size and shape which, in turn, leads to strongly diminished or even suppressed DNA association. Therefore, photocycloaddition–cycloreversion sequences have a huge potential for the photoinduced, reversible deactivation and activation of ligand–DNA interactions, as will be shown with selected examples in this Concept Article. Specifically, heterostyryl and ‐stilbene derivatives are presented whose DNA–binding properties are efficiently switched in reversible [2+2] photocycloaddition reactions. In addition, the photocontrolled DNA–binding of anthracene derivatives and their heterocyclic benzo[b]quinolizinium analogues in a [4+4] photocycloaddition, as well as the use of this reaction as part of dual–mode switches in combination with redox‐active functionalities, are highlighted. Furthermore, examples of conjugates are provided, in which the photochromic unit is bound covalently to nucleic acids or proteins, such that the photocycloaddition reaction can be used for reversible photoinduced crosslinking, ligation, or inhibition of gene expression.

The Photosalient Effect and Thermochromic Luminescence Based on o‐Carborane‐Assisted π‐Stacking in the Crystalline State

AbstractHerein, we report the unique multiple‐stimuli responsiveness of anthracene‐tethered o‐carborane derivatives. We designed and synthesized anthracene derivatives with different substitution positions and numbers of the o‐carborane units. Two compounds had characteristic crystal structures involving the columnar π‐stacking structures of the anthracene units. From the analysis of crystalline‐state structure–property relationships, it was revealed that the crystals exhibited the photosalient effect accompanied by photochemical [4+4] cycloaddition reactions and temperature‐dependent photophysical dual‐emission properties including excimer emission of anthracene. Those properties were considered as non‐radiative and radiative deactivation pathways through the excimer formation in the excited state and the formation of excimer species was facilitated by the π‐stacking structure of anthracene units. Moreover, we found unusual temperature dependency on the occurrence of the photosalient effect. According to the data from variable temperature X‐ray crystallography, a strong correlation between lattice shrinkage and strain accumulation is suggested.

The Photosalient Effect and Thermochromic Luminescence Based on o-Carborane-Assisted π-Stacking in the Crystalline State.

Herein, we report the unique multiple-stimuli responsiveness of anthracene-tethered o-carborane derivatives. We designed and synthesized anthracene derivatives with different substitution positions and numbers of the o-carborane units. Two compounds had characteristic crystal structures involving the columnar π-stacking structures of the anthracene units. From the analysis of crystalline-state structure-property relationships, it was revealed that the crystals exhibited the photosalient effect accompanied by photochemical [4+4] cycloaddition reactions and temperature-dependent photophysical dual-emission properties including excimer emission of anthracene. Those properties were considered as non-radiative and radiative deactivation pathways through the excimer formation in the excited state and the formation of excimer species was facilitated by the π-stacking structure of anthracene units. Moreover, we found unusual temperature dependency on the occurrence of the photosalient effect. According to the data from variable temperature X-ray crystallography, a strong correlation between lattice shrinkage and strain accumulation is suggested.

Anthracene-triphenylamine materials with high luminance and negligible efficiency roll-off for organic light-emitting diodes

Two novel anthracene-triphenylamine emitters, TPA-tBuANT and TPA-PyrANT, were synthesized efficiently by the coupling reactions of anthracene and triphenylamine derivatives. They emit blue-green light in the diluted solutions, having emission peaks at 488 and 510 nm, and exhibit high photoluminescence fluorescence quantum efficiency (PLQY) of 53% and 80%, respectively. Their PLQY were 19% and 49% in solid states at 470 and 487 nm, respectively. Employing TPA-tBuANT as an emitter, the maximum external quantum efficiencies (EQEs) were up to 4.1% in the non-doped devices of organic light-emitting diodes (OLEDs) and 5.2% in the doped devices. The maximum EQEs of the devices based on TPA-PyrANT were 4.5% for non-doped devices and 5.6% for the doped devices. The devices all exhibit negligible efficiency roll-off.

Enhancement of lifetime in blue triplet-triplet-fusion organic light-emitting diodes with fluorenyl amine- and triphenyl silane-based electron blocking layers

We report fluorenyl amine-based electron blocking layers (EBLs) N,9,9-triphenyl-N-(4′-(triphenylsilyl)-[1,1′-biphenyl]−4-yl)−9 H-fluoren-2-amine (P-pSi-DPFA), N,9,9-triphenyl-N-(3-(triphenylsilyl)phenyl)−9 H-fluoren-2-amine (P-mSi-DPFA), and N-([1,1′-biphenyl]−4-yl)−9,9-diphenyl-N-(3-(triphenylsilyl)phenyl)−9 H-fluoren-2-amine (BP-mSi-DPFA) that prevent intermolecular interactions with emissive layer (EML). Triplet-triplet fusion (TTF)-based organic light-emitting diodes (OLEDs) use anthracene derivatives as hosts, and due to the electron-rich nature of anthracene core, the recombination zone is predominantly formed at the EBL/EML interface. Therefore, it is important to control the intermolecular interaction between EBL and EML while also having an EBL with suitable hole transport characteristics and an appropriate highest occupied molecular orbital (HOMO) level. We developed TTF-based OLED achieving up to 1489 hours (LT50 at 500 cd/m2) using P-pSi-DPFA as the EBL, securing hole transport characteristics through a fluorenyl amine core, and preventing unwanted intermolecular interactions with the EML by substituting triphenyl silane into the amine core.

Green titanium dioxide (TiO2) nanoparticles assisted biodegradation of anthracene employing Serratia quinivorans HP5.

The anthracene biodegradation potential of Serratia quinivorans HP5 was studied under a controlled laboratory environment. The green TiO2 nanoparticles (NPs) synthesized from Paenibacillus sp. HD1PAH was used to accelerate the biodegradation process. The synergistic application of TiO2 NPs and S. quinivorans HP5 resulted in a reduction of anthracene concentration by 1.2 folds in liquid-medium and 1.5 folds in contaminated soil. Gas-chromatography and mass-spectrometric investigation showed the production of four anthracene derivatives, namely 1,2-anthracene dihydrodiol, 6,7-benzocoumarin, anthrone, and 9,10-anthraquinoneat the termination of experimental periods. Furthermore, bacterial biomass increased by 23.3 folds in the presence of TiO2 NPs, and overall soil enzyme activities were enhanced by 4.2 folds in the treated samples. In addition, there was a negative correlation observed between the biomass of S. quinivorans HP5 and the concentrations of anthracene, suggesting the involvement of bacterium in anthracene biodegradation processes. The degradation pathway of anthracene revealed its transformation into the less toxic compound 9,10-anthraquinone. Overall, this study elucidates a novel biodegradation pathway for anthracene and highlights the potential of nano-assisted bacterial remediation as a promising approach for environmental cleanup.

Excimer emission from polycyclic arenes bearing triphenylmethyl group: Solid-state fluorescence, mechanofluorochromism, aggregation-induced emission and cell imaging application

The excimer emission based on discrete π-stacked dimers of polycyclic π-systems has generated significant interest in the structure-luminescence relationship of excimers owing to their ultra-large Stokes shift. Herein, a series of excimer emissive luminogens were obtained by conjugating different polycyclic aromatic aldehydes (anthraldehyde, pyrenealdehyde and perylenealdehyde) with triphenylmethylamine. In crystalline states, all the molecules were arranged in the form of π-stacked arene dimers which were spatially isolated from each other by the bulky triphenylmethyl groups, and thus emitted bright excimer emission. The anthracene and pyrene derivatives showed fluorescence enhancement responses to grinding and the enhanced fluorescence could recover to the original state upon heating. The aggregation-induced emission (AIE) properties of them were dependent on the shapes and sizes of the polycyclic aromatic groups. The pyrene derivative showed the most excellent excimer-based AIE behavior among them. All of them were more apt to exhibit the excimer emission when formed nanoparticles with pluronic F-127 than that without pluronic F-127. Furthermore, PETP was utilized for bioimaging of living Hela cells and the high-resolution image was observed.

Terpenoids and phenolic compounds as biologically active compounds of medicinal plants with diuretic effect

The aim of the study was to summarize and systematize the literature data, as well as the results of the carried out research in the field of medicinal plants used as diuretics in the Russian Federation and abroad.Materials and methods. During the search for this review article materials, the abstract databases of PubMed, Google Scholar, as well as the ResearchGate and elibrary.ru were used. The search was carried out according to the publications for the period from 2005 to 2023. The keywords were as follows: herbal diuretics, diuretic drugs, kidney diseases, types of medicinal plant raw materials. The data from the authors’ previous scientific research on the analysis of the diuretic properties of certain types of medicinal plant raw materials, as well as individual substances of a phenolic nature isolated from them (simple phenols, flavonoids), were also reviewed.Results. It was determined that the diuretic activity of most of the medicinal plants used, is due to such groups of biologically active compounds as terpenoids (essential oils and saponins), simple phenols, flavonoids and anthracene derivatives related to the secondary metabolites. It has been shown that, despite the fact that many herbal diuretics have concomitant anti-inflammatory, antimicrobial, antiviral, antihistamine and other properties relevant from the point of view of etiology and pathogenesis of the disease, it is reasonable to use them as part of collections of medicinal plants and other combined medicinal herbal preparations, as this is in accordance with the global trend. The types of medicinal plant raw materials that can be a promising source of new diuretic herbal medicines, have been examined in this review.Conclusion. It has been determined that terpenoids and phenolic compounds make the greatest contribution to the manifestation of the diuretic activity of medicinal herbal preparations, among which the greatest structural diversity is noted for flavonoids. It has been established that in the composition of any drug, taking into account the peculiarities of etiology and pathogenesis of the disease, herbal diuretics can be both the main drug and an auxiliary component. The expediency of using medicinal plant raw materials with a diuretic effect as part of collections of medicinal plants and other combined preparations used in the treatment of kidney and urinary tract diseases has been also substantiated.

Emission Enhancement of Anthracene Derivative Caused by a Dramatic Molecular Orbital Change on the Nanosheet Surface

Emission Enhancement of Anthracene Derivative Caused by a Dramatic Molecular Orbital Change on the Nanosheet Surface

Mechanofluorochromic Properties of 1,4-Diphenylanthracene Derivatives with Hypsochromic Shift.

Several types of 1,4-diphenylanthracene derivatives 1-4 were prepared, and their photophysical properties were observed in the solid and solution states. Interestingly, the CN-group-substituted 1,4-diphenylanthracene derivative 2 was found to exhibit a higher fluorescence quantum yield (ϕf = 0.71) in the solid state than in the solution state, probably due to the formation of an intermolecular Ar-CN⋯H-Ar hydrogen bond and antiparallel type locked packing structure in the solid state. Furthermore, for some derivatives, an increase in the fluorescence quantum yield was observed in the PMMA film (1 wt%) over both the solid state and the solution state. More interestingly, some of the 1,4-diphenylanthracene derivatives exhibited unusual mechanofluorochromic properties with a "hypsochromic shift" in luminous color depending on the substituents of the phenyl group, and with the derivatives having CF3, OMe, CN, and two F substituents (1d-1f, 2-4) showing a significant luminous color change with a "hypsochromic shift" after grinding. However, no change in the luminous color was observed for the derivatives having H, Me, and one F substituent (1a-1c), and especially for some of the CN-substituted derivatives, a reversible luminous color change with a "hypsochromic shift" was observed, probably due to the formation of an antiparallel type packing structure. These "hypsochromic" anthracene derivatives could probably be utilized as new mechanofluorochromic materials.

Anthracene derivatives with strong spin-orbit coupling and efficient high-lying reverse intersystem crossing beyond the El-Sayed rule.

The attention to materials with hot exciton channel and triplet-triplet fusion (TTF) mediated high-lying reverse intersystem crossing (hRISC) has been raised for their ability to convert non-emissive 'dark' triplets into radiative singlet excitons. This spin conversion process results in high exciton utilization efficiency (EUE) that exceeds the theoretical limits. Notably, it is known that such spin conversion processes from the high-lying excited triplet to the singlet state are facilitated by the orthogonal orbital transition effect governed by the El-Sayed's rule. In this study, an anthracene derivative with indenoquinoline substituent 7,7-dimethyl-9-(10-(4-(naphthalen-1-yl)phenyl)anthracen-9-yl)-7H-indeno[1,2-f]quinoline (2MIQ-NPA) was synthesized and analyzed to investigate whether the hRISC process occurs in these molecules, even when the El-Sayed's rule is not followed. The hRISC channels of the emitter were fully unraveled through DFT calculations and experiments, which were quantitatively subdivided using transient electroluminescence measurements. The results showed that 2MIQ-NPA, which does not follow the El-Sayed's rule and has a relatively strong spin-orbit coupling matrix element of 0.116 cm-1 between the high-lying triplet state of T4 and the lowest singlet state of S1, effectively converted triplet excitons into singlet excitons with an EUE of 64.3%, contributed by a direct hot exciton channel of 19.2% and a TTF-mediated hot exciton channel of 15.1%. Despite the low outcoupling efficiency, the non-doped device with 2MIQ-NPA achieved an excellent device performance with an external quantum efficiency of 7.0%.

Correction: Orthogonal anthracene and pyrene derivatives for efficient pure deep-blue organic light-emitting diodes

Correction for ‘Orthogonal anthracene and pyrene derivatives for efficient pure deep-blue organic light-emitting diodes’ by He Jiang et al., J. Mater. Chem. C, 2023, 11, 6438–6443, https://doi.org/10.1039/D3TC00594A.

High-performance functionalized anthracene organic supercapacitors

An asymmetric organic supercapacitor exhibiting excellent electrochemical behavior is constructed using an anthracene derivative as a key component, exploiting synergy between the redox capabilities and charge transport.

Radiative pumping in a strongly coupled microcavity filled with a neat molecular film showing excimer emission.

Strong light-matter interactions have attracted much attention as a means to control the physical/chemical properties of organic semiconducting materials with light-matter hybrids called polaritons. To unveil the processes under strong coupling, studies on the dynamics of polaritons are of particular importance. While highly condensed molecular materials with large dipole density are ideal to achieve strong coupling, the emission properties of such films often become a mixture of monomeric and excimeric components, making the role of excimers unclear. Here, we use amorphous neat films of a new bis(phenylethynyl anthracene) derivative showing only excimer emission and investigate the excited-state dynamics of a series of strongly coupled microcavities, with each cavity being characterised by a different exciton-photon detuning. A time-resolved photoluminescence study shows that the excimer radiatively pumps the lower polariton in the relaxation process and the decay profile reflects the density of states. The delayed emission derived from triplet-triplet annihilation is not sensitive to the cavity environment, possibly due to the rapid excimer formation. Our results highlight the importance of controlling intermolecular interactions towards rational design of organic exciton-polariton devices, whose performance depends on efficient polariton relaxation pathways.

Smart emissive hybrid dynamer and nanocomposite made of complementary organic and inorganic emitters combined via a supramolecular Janus synthon

Blue-emitting anthracene derivatives are associated via hydrogen bonds to a red-emitting [Mo6I8(OCOC2F5)6]2− anion leading, once embedded in PMMA, to films whose emission color depends on the irradiation power and time.