Unexpected Formation Research Articles

Synthesis and Reactivity of an Aluminium N-heterocyclic Aminal.

Tethered N-heterocyclic carbenes (NHCs) are an emerging class of ligand, as they feature all the desirable aspects of NHCs (ease of synthesis, high tunabilty) but also enable metal-ligand cooperativity when combined with Lewis acidic metal centres due to the donor-acceptor nature of the complexes formed. Herein we report a simple ethoxy-tethered NHC for the stabilisation of Al(III) hydrides, resulting in the unexpected formation of a bicyclic N-heterocyclic aminal (1). Compound 1 behaves as a metal hydride, capable of reducing benzophenone and carbodiimide to yield compounds 2 and 3, respectively. Furthermore, we show that 1 behaves as an efficient catalyst in the dehydrocoupling of amine-boranes due to the hemi-labile nature of the supporting ligand.

Competitive Charge Separation Pathways in a Flexible Molecular Folda-Dimer.

We report the photophysical properties of a molecular folda-dimer system PDI-AnEt2-PDI, where the electron-donating N,N-diethylaniline (AnEt2) moiety bridges two electron-accepting perylene diimide (PDI) chromophores. The conformationally flexible PDI-AnEt2-PDI adopts either an open (two PDIs far apart) or folded (two PDIs within π-stacking distance) conformation, depending on the solvent environment. We characterized the photoinduced charge separation dynamics of both open and folded forms in solvents of varying polarity. The open form undergoes charge separation to give PDI•--AnEt2•+-PDI (Bridge electron transfer) independent of solvent polarity. The folded form exhibits two charge separation photoproducts, yielding both PDI•--AnEt2•+-PDI and PDI•--AnEt2-PDI•+, the latter of which is formed via symmetry-breaking charge separation (SBCS) between the two π-stacked PDI chromophores. Our results further indicate that the conformational flexibility of the folda-dimer leads to unexpected excimer formation in some open form conditions. In contrast, no excimer formation is observed in the folded form, indicating that this geometry preferentially yields the SBCS instead. Our results provide insight into how conformationally flexible folda-dimer systems can be designed and built to tune competitive photophysical pathways.

Switching between P-acylation and O-acylation of H-phosphonates with chloroformates by changing acyl pyridinium and acyl ammonium ions in a microflow reactor.

We report the first switchable acylation of H-phosphonate with chloroformate. The acylation site (P vs. O) in H-phosphonate was switched by changing the acyl pyridinium/ammonium ions. Unexpected phosphite formation was observed during the O-acylation of H-phosphonate. Twenty-six structurally diverse phosphotriesters and phosphonoformate esters were synthesized in microflow reactors.

Influence of arylalkyl amines on the formation of hybrid CsPbBr3 nanocrystals via a modified LARP method.

Perovskite nanocrystals have attracted much attention in the last ten years due to their different applications, especially in the photovoltaic domain and LED performance. In this large family of perovskite nanocrystals, CsPbBr3 nanocrystals are attractive nanomaterials because they are good candidates for obtaining green emissions and exploring new synthesis routes. In this context, controlling the nanometric scale's morphology, particularly the size and monodispersity, is fundamental for exploring their photophysical properties and final applications. Currently, the nanometric size of nanocrystals is ensured by the presence of oleic acid and oleylamine molecules, in using Hot Injection (HI) or ligand-assisted reprecipitation (LARP) methods. If oleic acid plays a fundamental role, oleylamine can be easily substituted by other amino molecules, opening the way for the functionalization of CsPbBr3 nanocrystals and the obtention of new hybrid perovskite nanocrystal families. In this article, we describe the synthesis, by soft chemistry, of a new family of hybrid organic-inorganic CsPbBr3 nanocrystals, functionalized by aryl-alkylamine (AAA) molecules, through the modified LARP method. We highlight the mechanism for cutting submicron crystals into nanocrystals, using aryl-alkylamine molecules like scissors. The impact of these amino molecules on the final nanocrystals leads to different nanocrystal morphologies (nanocubes, nanosheets, or nanorods) and structures (monoclinic, rhombohedral, or tetragonal). In addition, this modified LARP method highlights, under certain experimental conditions, an unexpected formation of PbO ribbons.

Coordination of azol(in)ium dithiocarboxylate ligands to Au(III): unexpected formation of a novel family of cyclometallated Au(III) complexes, DFT calculations and catalytic studies.

A series of cyclometallated gold(III) complexes 21-27 of general formula [Au(dppta)(azdtc)Cl] (dppta = N,N-diisopropyl-P,P-diphenylphosphinothioic amide-κ2C,S; azdtc = azol(in)ium-2-dithiocarboxylate-κ1S) were prepared and characterized by spectroscopic and diffractometric techniques. Treatment of [Au(dppta)(azdtc)Cl] complexes with methanol led to their quantitative transformation into a novel family of (C^S, S^S)-cyclometallated gold(III) complexes of general formula [Au(dppta)(azmtd)] (azmdt = azol(in)ium-2-(methoxy)methanedithiol-κ2S,S) 28-34. All the [Au(dppta)(azdtc)Cl] complexes 21-27 catalyzed the alkylation of indoles, whereas [Au(dppta)(azmtd)] complexes 28-34 were inactive. Among the synthesized derivatives, complex 22 displayed the highest catalytic activity, leading to a series of functionalized indoles in excellent yields.

Nanoscale liquid Al phase formation through beam heating of MgAl2O4 in TEM.

In this study, electron-beam irradiation of a MgAl2O4 single-crystalline thin-film specimen in a transmission electron microscope reveals an unexpected formation of nanoscale liquid Al droplets. Despite the comparable melting temperatures of Mg and Al, the resulting liquid phase is predominantly composed of Al. This predominant presence of Al in the liquid phase is attributed to the selective evaporation of Mg, driven by its higher vapor pressure at elevated temperatures. Our observations suggest a correlation between electron-beam irradiation and a subsequent rise in specimen temperature. In particular, the observed melting of Al defies explanation by the widely accepted mechanism that attributes specimen heating to electron-energy loss, given the negligible energy deposited as determined by the collision stopping power. Instead, we suggest that the significant specimen heating is due to Auger excitation, a process known to deposit substantial energy. This contention is supported by a quantitative heat-transfer finite element analysis.

Kaskadenreaktionen von aryl‐substituierten terminalen Alkinen unter Beteiligung von in situ erzeugten α‐Imino‐Goldcarbenen

AbstractWir berichten über eine effiziente, hochselektive und divergente Synthesemethode zur Herstellung von 2‐substituierten Indolen und aryl‐anellierten Carbazolen über die intermolekulare Erzeugung von α‐Imino‐Goldcarbenen aus terminalen Alkinen oder Diinen in Kombination mit Sulfiliminen. Wichtig ist, dass die Tandemreaktion durch eine intermolekulare Goldcarbenbildung/C−H‐ Anellierung, gefolgt von der Aktivierung eines zweiten Alkins, die zu einer 6‐endo‐dig‐Zyklisierung führt, abläuft, was sich deutlich von früheren Ansätzen der dualen Aktivierung oder 1,6‐Carbenverschiebung für Diin‐Systeme unterscheidet. Im Falle von ortho‐Alkinylanilin als Ausgangsmaterial wurde eine unerwartete regioselektive Bildung der Indolkomponente über den intermolekularen Weg anstelle einer intramolekularen Hydroaminierung entdeckt. Diese Reaktivität ebnete den Weg für eine Eintopfsynthese des 11H‐Indolo‐[3,2‐c]‐Chinolin‐Gerüsts, indem das gebildete Aminoindol für eine anschließende Pictet–Spengler‐Reaktion mit Aldehyden genutzt wurde. Die photophysikalischen Eigenschaften der Carbazole zeigten eine gute violett‐blaue Emission mit Quantenausbeuten von bis zu 40 %.

Cascade Reactions of Aryl-Substituted Terminal Alkynes Involving in Situ-Generated α-Imino Gold Carbenes.

An efficient, highly selective and divergent synthetic method to construct 2-substituted indoles and aryl-annulated carbazoles via the intermolecular generation of α-imino gold carbenes from terminal alkynes or diynes in combination with sulfilimines is disclosed. Importantly, the tandem reaction is proposed to proceed through an intermolecular gold carbene generation/C-H annulation followed by the activation of a second alkyne leading to 6-endo-dig cyclization, which is significantly different from previous dual activation or 1,6-carbene shift approaches for diyne systems. In the case of ortho-alkynylaniline as starting material, an unexpected regioselective formation of the indole moiety via the intermolecular path, instead of intramolecular hydroamination was discovered. This reactivity paved the way for a one-pot synthesis of the 11H-indolo [3,2-c] quinoline scaffold by exploiting the formed amino indole for a subsequent Pictet-Spengler reaction with aldehydes. The photophysical properties of the carbazoles indicated good violet-blue emission with quantum yields up to 40 %.

Unexpected hydroxyl radical production in brewed tea under sunlight.

Tea is one of the world's most popular and widely consumed beverages. It is a common pastime to enjoy a cup of tea in the sunshine. However, little attention has been given to understanding the possible photochemical reactions occurring beneath the calm surface of brewed tea. Epigallocatechin gallate (EGCG), which is widely used in food and beverages, is the most significant active ingredient found in tea. In this study, we investigated the presence of free radicals in both an aqueous EGCG solution and brewed tea under simulated sunlight conditions. To our surprise, we unexpectedly observed the production of hydroxyl radicals (•OH) in brewed tea. It was found that sunlight irradiation played a critical role in the formation of •OH, independent of the presence of metal ions. Furthermore, we demonstrated that the •OH generated from the EGCG aqueous solution induced cell cytotoxicity and DNA damage in vitro. Considering the crucial role of •OH in various fields, including human health and the environment, it is important to further explore the practical implications of •OH production in brewed tea under sunlight. In summary, our study unveils the unexpected formation of •OH in brewed tea and emphasizes the significance of sunlight-induced reactions. The observed cytotoxic and DNA-damaging effects of •OH emphasize the importance of understanding the potential health consequences associated with tea consumption. Further research in this area will contribute to a better understanding of the broader implications of •OH production in brewed tea under sunlight.

Decomposed defect formation energy for analysis of doping process: The case of n-type and p-type doping of β-FeSi2

Defect formation energy governs the thermodynamics of a specific dopant within the host material. Here, we introduce an approach to decomposing the defect formation energy into intuitive components, each representing a distinct physical step in the process of defect formation. Through this approach, we illustrate that adhering solely to conventional criteria, such as ionic radius, may overlook potential dopants. Taking β-FeSi2, a promising high-temperature thermoelectric material, as an example, we demonstrate that non-intuitive chemical interactions can play a more significant role in lowering the defect formation energy. As a result, Ir on Fe site is found to exhibit unexpected low defect formation energy among the 26 candidate dopants and has been employed in experiment to enhance the thermoelectric figure of merit of n-type β-FeSi2. The understanding gained from this work could be of general interest for addressing the doping limit issue for other potential thermoelectric materials.

Utilizing Baylis–Hillman Adducts Followed by Michael Addition/Elimination Reaction for the Synthesis of Unusual Conformationally Stable Molecules Governed by Aromatic Interactions

AbstractThe compounds under investigation sought a new approach to synthesis via the Baylis‐Hillman (B−H) and Michael addition reactions. The product formation‘s legitimacy was tested using a repeat reaction with many different nucleophiles. The additional stability of the product via aromatic π⋅⋅⋅π and C−H⋅⋅⋅π interactions may result in unexpected product formation in diverse reactions undertaken utilizing different starting materials. This study suggests that weak interaction not only provides selectivity during reactions but also modifies the result.

Pump‐Induced Terahertz Conductivity Response and Peculiar Bound State in Mn3Si2Te6

AbstractThe significant enhancement of ultrafast terahertz optical conductivity and the unexpected formation of a polaronic‐like state in semiconductor Mn3Si2Te6 at room temperature are reported. With the absorption of pump photons, the low‐frequency terahertz photoconductivity spectrum exhibits a significant rise, quickly forming a broad peak and subsequently shifting to higher energy. The short‐lived nature of the broad peak, as well as the distribution of optical constants, strongly points toward a transient polaron mechanism. This study not only provides profound insights into the remarkable photoelectric response of Mn3Si2Te6 but also highlights its significant potential for future photoelectric applications.

Analisis Silistika Pada Puisi “Kau Ini Bagaimana Atau Aku Harus Bagaimana” Karya Gus Mus

Literary work is a study of stylistics that uses literary language styles as a medium to discover its aesthetic value. Stylistics is the science of using language in literary works. The use of specific language styles in literary works created by the author himself. Therefore, the objective of this research analysis aims to determine the use of language styles (figure of speech), describe the diction and message to be conveyed in the poem "How are you or what should I do" by KH Mustofa Bisri. Based on the stylistic approach put forward as the basis for the theoretical study used in the analysis. This type of research uses qualitative methods. The theory used is stylistic theory with a stylistic approach. This is able to convey messages indirectly to the reader, what attitudes and behavior should be carried out. Based on the results of the analysis of the poem You Are How or I Have to How by KH Mustofa Bisri which highlights various aspects of strong and unexpected word formation in order to find out about the implied meaning that KH Mustofa Bisri wants to convey through the application of language styles (figure of speech), so that the meaning is hidden in The poem "How are you or what should I do" can be clearly expressed by the author. The author found the language styles of association, irony, parallelism and paradox, there are 6 language styles (figure of speech) which are divided into; 1 association, 2 ironies, 2 parallelisms and 1 paradox. Based on the results of the analysis, from the poem "How are you or what should I do" by Gus Mus, 6 language styles were obtained.

Synthesis of Polycyclic Arenes Composed of Four-, Five-, Six-, and Eight-Membered Rings via an Unexpected Four-Membered Ring Formation Reaction.

The synthesis of polycyclic arenes composed of four-, five-, six-, and eight-membered rings via an unexpected four-membered ring formation reaction is reported. The carbonylation of an octalithiated tetraphenylene yielded a tricarbonylated arene containing a four-membered ring or a tetracarbonylated one, depending on the carbonyl reagents. The structures were determined by X-ray crystallography, and their electronic properties were examined by using absorption spectroscopy and cyclic voltammetry. The antiaromaticity of the four-, five-, and eight-membered rings of these compounds was studied by theoretical calculations.

Directing Intrinsic Chirality in Gold Nanoclusters: Preferential Formation of Stable Enantiopure Clusters in High Yield and Experimentally Unveiling the "Super" Chirality of Au144.

Chiral gold nanoclusters offer significant potential for exploring chirality at a fundamental level and for exploiting their applications in sensing and catalysis. However, their widespread use is impeded by low yields in synthesis, tedious separation procedures of their enantiomeric forms, and limited thermal stability. In this study, we investigated the direct synthesis of enantiopure chiral nanoclusters using the chiral ligand 2-MeBuSH in the fabrication of Au25, Au38, and Au144 nanoclusters. Notably, this approach leads to the unexpected formation of intrinsically chiral clusters with high yields for chiral Au38 and Au144 nanoclusters. Experimental evaluation of chiral activity by circular dichroism (CD) spectroscopy corroborates previous theoretical calculations, highlighting the stronger CD signal exhibited by Au144 compared to Au38 or Au25. Furthermore, the formation of a single enantiomeric form is experimentally confirmed by comparing it with intrinsically chiral Au38(2-PET)24 (2-PET: 2-phenylethanethiol) and is supported theoretically for both Au38 and Au144. Moreover, the prepared chiral clusters show stability against diastereoisomerization, up to temperatures of 80 °C. Thus, our findings not only demonstrate the selective preparation of enantiopure, intrinsically chiral, and highly stable thiolate-protected Au nanoclusters through careful ligand design but also support the predicted "super" chirality in the Au144 cluster, encompassing hierarchical chirality in ligands, staple configuration, and core structure.

Investigation into the electrochemical advanced oxidation of p-arsanilic acid: Peculiar role of electrolytes and unexpected formation of coupling byproducts

Although banned in some countries, p-arsanilic acid (ASA) is still widely used as feed additive in poultry production. As a result, ASA is usually released into the aquatic environment without any treatments. Although ASA exhibits low toxicity, it can be transformed into highly toxic aromatic amines and inorganic arsenic species (As (V) as H2AsO4− and HAsO42−) under natural environmental conditions. Hence, it is necessary to develop efficient technologies for its removal or degradation. In this contribution, electrochemical advanced oxidation technology with boron-doped diamond (BDD) had been initially used to degrade ASA pollutants. A five-level central composite rotatable design (CCRD) was implemented to optimize the various influencing factors involved, among applied current density, NaCl concentration, Na2SO4 concentration and NaHCO3 concentration on the oxidation efficiency; the latter was assessed in terms of ASA degradation percentage. The results obtained highlighted the unique and important roles of electrolytes during the electrolytic oxidations. Meanwhile, the major degradation byproducts detected were also strongly dependent on the electrolyte adopted. In particular, several oligomer byproducts with novel structures were initially identified in BDD-treated ASA solutions. Two different electrochemical transformation pathways of ASA on BDD anode were thus proposed. This study demonstrated the effectiveness of BDD technology in the degradation of ASA, as well as the potential minor risk of its application in actual ASA wastewater treatment.

Stereoselective synthesis of syn-meso-cyclooctanetetraol, bromo-, and oxabicyclic amino-alcohol derivatives

The first synthesis of syn-meso-cyclooctane-1,2,3,4-tetraol isomer, a new bromocyclooctanetriol, and oxabicyclic amino-alcohol derivatives of them starting from cis,cis-1,3-cyclooctadiene is described. For the construction of a cyclooctane-1,2,3,4-tetraol skeleton with all the syn hydroxyl groups, cyclooctene endoperoxide was used as the key compound. Epoxidation of the endoperoxide followed by hydrogenation of the peroxide group gave the corresponding syn-epoxy-diol, which was hydrolysed with HBr(g) in methanol to produce a bromotriol compound that is a potentially important cyclitol for the versatile synthesis of different cyclitols and aminocyclitols. Reaction of bromotriacetate with AgClO4 afforded the target syn-meso-tetrol as the sole product. Treated of azidoepoxide, which was the second key compound, with HBr(g) in methanol resulted in the unexpected formation of an oxabicyclic azido-alcohol derivative.

Unexpected but prominent imines formation in Beckmann rearrangement of (spiro)pyranocoumarin oximes

This paper presents the successful implementation of Beckmann rearrangement on a series of (spiro)pyranocoumarin oximes in polyphosphoric acid (PPA) medium. The method demonstrated excellent proficiency in the synthesis of unexpected imines as major products and amides as minor products. The labeled 15NH2OH·HCl control experiment yielded oxime and rearrangement products that incorporated the 15N label. Furthermore, we have proposed a possible rearrangement mechanism. NMR spectroscopy data (correlation HMBC and 15N NMR) confirmed the structure of the synthesized products. These findings provide a new and efficient approach for constructing complex imines with diverse applications in synthetic organic chemistry.

Unexpected Dioxin Formation During Digestion of Soil with Oxidizing Acids.

Dioxins, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), are among the most toxic unintentionally produced persistent organic pollutants, and their emission is of great concern. Herein, we discovered abundant dioxin formation in soil and various organic carbon-containing matrices after digestion with aqua regia. Σ17PCDD/Fs concentrations were in the range of 66.6-142,834 pg/g dw (5.6-17,021 pg WHO2005-TEQ/g dw) in 19 soil samples after digestion with aqua regia for 6 h. Σ17PCDD/Fs concentration was significantly and positively correlated with soil organic carbon content (R2 = 0.89; p < 0.01). Compared with cellulose and lignin, humic acid served as an important organic matter component that was converted to PCDD/Fs during soil digestion. Strong oxidation and production of reactive chlorine by aqua regia may be the key factors in the formation of PCDD/Fs. The yearly emission of PCDD/Fs due to digestion with strong acids by the inspection and testing industry was estimated to be 83.8 g TEQ in China in 2021 based on the highest level, which was ∼0.9% of the total dioxin inventory in China. Great attention should be paid to unexpected dioxin formation during digestion processes considering the potential risk of release from laboratories and enterprises.

3+2]-Cycloaddition Reactions of gem-Difluorocyclopropenes with Azomethine Ylides - Access to Novel Fluorinated Scaffolds.

The introduction of fluorinated moieties into drugs as well as the increase of their overall three-dimensionality have become key strategies amongst medicinal chemists to generate sets of compounds with favorable drug-like properties. However, the introduction of fluorinated cyclopropane ring systems which combines both strategies is not widely exploited to date. This paper reports synthetic strategies exploiting the reactivity of gem-difluorocyclopropenes in dipolar cycloaddition reactions with azomethine ylides to afford sets of new fluorine-containing 3-azabicyclo[3.1.0]hexanes. In addition, the unexpected formation of complex trifluorinated scaffolds arising from proline esters and gem-difluorocyclopropenes is highlighted along with computational studies to elucidate the underlying mechanism. This study presents new avenues towards pharmaceutically relevant fluorinated 3-azabicyclo[3.1.0]hexanes that are accessible via robust and short synthetic sequences.