Radical Salts Research Articles

Radical cation salts of BETS and ET with dicyanamidocuprate anions demonstrating metal-insulator and semiconductor–semiconductor transitions

Electrocrystallization of bis(ethylenedithio)tetraselenafulvalene (BETS) and bis(ethylenedithio)tetrathiafulvalene (ET) in the presence of an electrolyte (Ph4P)[Cu(dca)]3⋅H2O [(dca) = N(CN)2] has been studied using different solvents. A new organic metal (BETS)2Cu(dca)3 (1), and the first radical cation salt with 3D dicyanamidocuprate anion, incorporating both diamagnetic Cu1+ and paramagnetic Cu2+atoms, (ET)2Cu1.8(dca)4 (2) have been obtained. Crystal structure, conducting properties of both salts, as well as the electronic structure of 2 and its structural analog (ET)2CuMn(dca)4 (3) were analysed. The salts 1 and 2 have layered structures. In contrast to the BETS radical cation salt 1, complex 2 is characterized by the presence of a 3D polymeric anion built into the ET radical cation layers. At ambient pressure, the resistance of the crystals 1 shows semimetal behaviour down to 30 K. Below 30 K, the resistance sharply increases and the sample becomes insulating. The application of a pressure of about 3 kbar suppresses the metal-insulator transition. The salt 2 undergoes a semiconductor I - semiconductor II phase transition, which is manifested by a jump in the resistance and a hysteresis in the R(T) curves in a very large temperature range (185 – 250 K). The phase transition is accompanied by changes in the charge state of the ET molecules, and notable structure changes in the anion layer, especially in the environment of Cu2+. For the salt 3 the calculated selfconsistent charges show upon cooling a sharp increase of charge order between 291 K and 285 K.

Optimized supercritical CO2 extraction conditions on yield and quality of torch ginger (Etlingera elatior (Jack) R.M. Smith) inflorescence essential oil

Natural preservatives derived from plant sources have been actively studied as an alternative to synthetic materials. Various extraction methods had been done to utilize the torch ginger plant for food, nutraceutical and pharmaceutical applications. Supercritical carbon dioxide (SC−CO2) extraction is a sustainable green technology to extract high-purity oil with high aromatic compound content. This study aims to optimize the SC−CO2 extraction conditions on high yield and strong antioxidant activity of torch ginger (Etlingera elatior) inflorescence essential oil (TGIEO). Response surface methodology in combination with central composite design was employed and two independent variables, pressure (83.6–366.4 bar) and temperature (34.7–57.3 °C) were analysed to optimize the response variables. Pressure was observed as the most significant parameter affecting the yield and antioxidant activity. The optimized SC−CO2 extraction conditions were pressure 286.4 bar and temperature 57.3 °C. The experimental values of response variables at these SC−CO2 extraction conditions match well with the predicted values which confirm the model validity. The TGIEO showed high diphenyl-2-picryl-hydrazyl and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt radical scavenging activity. Antimicrobial activity screening for TGIEO was done via disc diffusion assay and showed inhibition zone (11.5 ± 0.71 to 22.0 ± 2.83 mm) against six pathogenic bacteria (Bacillus subtilis, Staphylococcus aureus, Listeria monocytogenes, Salmonella typhi, Vibrio species and Escherichia coli). Listeria monocytogenes was observed as the most sensitive microorganism with minimal inhibitory concentration (0.16 mg/mL) and minimal bactericidal concentration (0.63 mg/mL) respectively. Compounds 1-dodecanol and lauryl acetate were identified as major constituent in TGIEO.

BNB-Doped Phenalenyls: Modular Synthesis, Optoelectronic Properties, and One-Electron Reduction.

A highly modular synthesis of BNB- and BOB-doped phenalenyls is presented. Treatment of the 1,8-naphthalenediyl-bridged boronic acid anhydride 1 with LiAlH4/Me3SiCl afforded the corresponding 1,8-naphthalenediyl-supported diborane(6) 2, which served as the starting material for all subsequent transformations. Upon addition of MesMgBr/Me3SiCl, 2 was readily converted to the tetraorganyl diborane(6) 5. The further heteroatoms were finally introduced through the reaction of 2 with (Me3Si)2NR' or 5 with H2NR' or H2O (R' = H, Me, p-Tol). A helically twisted, fully BNB-embedded PAH 11 was prepared by combining 2 with a dibrominated m-terphenylamine, followed by a Grignard-mediated double ring-closure reaction. All compounds devoid of B-H bonds show favorable optoelectronic properties, such as luminescence and reversible reduction behavior. In the case of the BNB-phenalenyl 7 (BMes, NMe), the radical-anion salt K[7•] was generated through chemical reduction with K metal and characterized by EPR spectroscopy. K[7•] is not long-term stable in a THF/c-hexane solution, but abstracts an H atom with formation of the diamagnetic BNB-doped 1H-phenalene K[7H].

Electrical Conductivity-Relay between Organic Charge-Transfer and Radical Salts toward Conductive Additive-Free Rechargeable Battery.

In recent years, organic electrode materials have been strongly considered for use in sustainable batteries. However, most organic electrode materials have low electrical conductivity and require a lot of conductive additives, which decrease the effective capacity based on the entire electrode weight/volume. In this study, we propose a novel electrical conductivity-relay system that imparts electrical conductivity to organic small molecular electrodes without any conductive additive throughout the charge/discharge cycles. It consists of the combination of the charge-transfer phenomenon in a pristine state and the formation of organic radical salts in redox states. Herein, we demonstrate this electrical conductivity-relay system using a simply mixed molecular crystal couple of tetrathiafulvalene (TTF) and tetracyanoquinodimethane (TCNQ) as a cathode without any conductive additive and aqueous sodium bromide as an electrolyte. During charge/discharge, the electrical conductivity of the cathode is supported by charge-transfer at the TTF/TCNQ interface and (TTF)Brn (0.7 ≤ n ≤ 0.8) and NaTCNQ radical salts, and the cathode exhibits a specific capacity of 112 mAh g-1 and a retention rate of 80.7% at the 30th cycle. Furthermore, the molecular crystal couple electrode of TTF and TCNQ shows better charge/discharge performance than the pure charge-transfer complex electrode, indicating that this system expands candidates for organic electrode materials to various pairs and mixing ratios of small molecules that do not form charge-transfer complexes.

Antioxidative and Neuroprotective Effects of the Cytochalasans From Endophytes

Six 10-indolyl-cytochalasans, chaetoglobosin F (1), chaetoglobosin Fex (2), chaetoglobosin E (3), cytoglobosin A (4), penochalasin C (5), and isochaetoglobosin D (6), and 2 10-phenyl-cytochalasans, cytochalasin H (7) and 18-methoxycytochalasin J (8) were isolated from 2 plant endophytes, Chaetomiun globosum WQ and Phomopsis sp. IFB-E060, respectively. These cytochalasans were investigated with radical-scavenging activity assay and hydrogen peroxide (H2O2)/ N-methyl-4-phenylpyridinium iodide (MPP+)-induced pheochromocytoma cell line 12 (PC12) cell models, respectively. Results showed that 7 compounds had antioxidative effects except 5, with scavenging 2,2-diphenyl-1-picrylhydrazyl radical effect 1 = 6= 7 > 2> 4 = 3 > 8 and scavenging 2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt radical effect 1 = 6 = 7 > 2 > 3 > 8 > 4. They could also inhibit H2O2/MPP+-induced damage in PC12 cells by increasing cell viability and decreasing lactate dehydrogenase release. Compounds 1, 6, and 7 exhibited the strongest antioxidative potencies, which are more potent than vitamin E. Additionally, antioxidative and neuroprotective effects of 1∼8 showed some structure–activity relationship. These findings would be useful for looking for cytochalasin-related new lead compounds or drugs to prevent and treat Parkinson’s disease.

Biotransformation of phenolics and metabolites and the change in antioxidant activity in kiwifruit induced by Lactobacillus plantarum fermentation.

Changes in antioxidant activity of fruit during fermentation are related to changes in the composition of phenolic acids and flavonoids. In this study, we investigated the effects of Lactobacillus plantarum on the phenolic profile, antioxidant activities, and metabolites of kiwifruit pulp. Lactobacillus plantarum fermentation increased scavenging activity of 1-diphenyl-2-picrylhydrazyl (DPPH) and 2,20-azinobis (3-ethylbenzothiazoline-6-sulphonic acid) diammonium salt (ABTS) radicals. The content of phenolics and flavonoids was increased after fermentation. Correlation analysis demonstrated that the phenolic and flavonoid content was responsible for increasing the scavenging activities of DPPH and ABTS. Lactobacillus plantarum influenced the phenolic profile of the pulp. Protocatechuic and chlorogenic acids were the predominant phenolic acids in fermented kiwifruit pulp. Gallic acid, chlorogenic acid, epicatechin, and catechins were degraded by L. plantarum. The content of 6,7-dihydroxy coumarin and p-coumaric acid, and especially protocatechuic acid, was increased by fermentation. Metabolic differences in lactic acid, fructose, phosphoric acid, gluconolactone, and sugar were evident between non-fermented and fermented kiwifruit. Lactobacillus plantarum fermentation increased antioxidant compounds and antioxidant activity in kiwifruit pulp. These results provide the foundation to target the functional benefits of L. plantarum-fermented kiwifruit pulp for further human, animal, and plant health applications. © 2020 Society of Chemical Industry.

The Crystal Structure of a RAS (N–CH3-2-NH2-5-Cl–Py)(TCNQ)(CH3CN) Solvate

The structure of the radical anion salt (RAS) of 7,7,8,8-tetracyanedimethane (TCNQ) with a cation based on 2-amin-5-chloro-pyridine (2-NH2-5-Cl–Py, Am), that is, (N–CH3-2-NH2-5-Cl–Py) (TCNQ) (CH3CN), (I) is presented. Unlike most TCNQ RASs, which contain flat TCNQ particle stacks, RAS I contains practically isolated (TCNQ)$$_{2}^{{2 - }}$$ π-dimers with unusually short distances between the planes in the dimers: 3.24 A. In the RAS I IR spectra special features are observed that correspond to the vibronic interactions of molecular vibrations.

Use of Phycobiliproteins from Atacama Cyanobacteria as Food Colorants in a Dairy Beverage Prototype.

The interest of the food industry in replacing artificial dyes with natural pigments has grown recently. Cyanobacterial phycobiliproteins (PBPs), phycoerythrin (PE) and phycocyanin (PC), are colored water-soluble proteins that are used as natural pigments. Additionally, red PE and blue PC have antioxidant capabilities. We have formulated a new food prototype based on PBP-fortified skim milk. PBPs from Andean cyanobacteria were purified by ammonium sulfate precipitation, ion-exchange chromatography, and freeze-drying. The stability of PE and PC was evaluated by changes in their absorption spectra at various pH (1–14) and temperature (0–80 °C) values. Purified PBPs showed chemical stability under pH values of 5 to 8 and at temperatures between 0 and 50 °C. The antioxidant property of PBP was confirmed by ABTS (2,2′-Azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt radical ion scavenging, and FRAP (Ferric Antioxidant Power) assays. The absence of PBP toxicity against Caenorhabditis elegans was confirmed up to 1 mg PBP/mL. Skim milk fortified with PE obtained a higher score after sensory tests. Thus, a functional food based on skim milk-containing cyanobacterial PBPs can be considered an innovative beverage for the food industry. PBPs were stable at an ultra-high temperature (138 °C and 4 s). PBP stability improvements by changes at its primary structure and the incorporation of freeze-dried PBPs into sachets should be considered as alternatives for their future commercialization.

INSIGHT INTO THE EFFECTS OF BAY-SUBSTITUENTS ON STABLE PERYLENE DIIMIDE RADICAL ANION SALTS

In previous work, the facile method to prepare perylene diimide radical anion salt by alkali treatment was reported. However, the effects of structure on synthetic process of perylene diimide radical anion salt, and the difference of response to Cu 2+ are not thoroughly understood. In this work, two bay-substituted perylene diimide derivatives radical anion salts have been synthesized and characterized in order to study the influence of the bay-substituted groups on the formation condition of the corresponding radical anion salt, and the sensitivity to Cu 2+. The result indicates that the perylene diimide with electron-donating groups (-O-Ph) at bay position was much easier to get the air-stable radical anion salts and had higher sensitivity to Cu 2+ compared to the perylene diimide with electron-withdrawing groups (-Br) at bay position.

Stabilization and isolation of radical cation and dication salts of a tetrathiafulvalene derivative functionalized with amino groups

The radical cation and dication salts of a tetrathiafulvalene derivative functionalized with amino groups have been stabilized and isolated by chemical oxidation. Comprehensive research on their structure–property relationship was fully performed.

Serendipitous isolation of a triazinone-based air stable organic radical: synthesis, crystal structure, and computation

Here we report the synthesis, isolation, and characterization of a dication salt, namely 4,6-bis(4,4′-bipyridinium)-1,3,5-triazin-2-one {12+(PF6)22−·2H2O1(PF6)2·2H2O}, and its radical cation salt, namely 4,6-bis(4,4′-bipyridinium)-1,3,5-triazin-2-one (1+˙PF6−1˙PF6).

In Vitro and In Vivo Antioxidative Activity against Radiation-Induced Damage and the Systematic Chemical Components of Different Extracts of Lagotis brevituba Maxim.

Lagotis brevituba Maxim is a perennial species distributed in the highlands of China, which has been used for more than 2000 years as a traditional Tibetan medicinal plant. However, no attention has been paid to the antioxidant activities of Lagotis brevituba Maxim in vitro or in vivo. Thus, this study aimed to evaluate the in vitro and in vivo antioxidant activity of Lagotis brevituba Maxim against radiation-induced damage as well as the systematic chemical components. To explore the relationship between the antioxidant activity and extraction solvent, Lagotis brevituba Maxim was extracted with three different solvents: methanol, water, and acetone. In antioxidant assays in vitro, the water extract had the strongest reducing power, 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) radical, and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity compared with the methanol and acetone extracts. However, the methanol extract was more potent in the β-carotene/linoleic acid cooxidation assay. In antioxidant assays in vivo, mice that were exposed to 6.0 Gy60Co γ-ray whole-body radiation on day 15 after administration of Lagotis brevituba Maxim decreased their level of malondialdehyde (MDA) in a dose-dependent manner compared with the control group, indicating that Lagotis brevituba Maxim had favorable antioxidant activities in vivo. In addition, a total of 44 compounds were tentatively identified by liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (LC-ESI-QTOF-MS/MS), including 19 flavonoids, 14 phenols, 8 phenylethanoid glycosides, 2 iridoid glycosides, and 1 carbohydrate. We obtained 25 compounds from plants in the genus Lagotis for the first time. These results suggested that Lagotis brevituba Maxim had potent antioxidant activity and could be explored as a novel natural antioxidant.

One-dimensional electronic systems: metal-chain complexes and organic conductors.

One-dimensional (1D) metal-chain complexes and organic conductors show many similarities as well as striking differences in structural and electronic properties, although constituent elements and orbitals that contribute to charge transfer in these systems are quite different. In this review, we highlighted the structural and electronic properties of neutral MMX-chain complexes (M = Pt2+/3+, X = I-) and tetramethyltetrathiafulvalene-based cation radical salts as typical examples of each group while comparing them with each other. This review primarily aims to construct a coherent body of knowledge of 1D electronic materials that might have been separately investigated. We have proposed future directions for the exploration of new and more advanced electronic materials not only having 1D character, but also residing in the dimensional crossover regime.

Chemical Characterization and Bioactivity of Extracts from Thymus mastichina: A Thymus with a Distinct Salvianolic Acid Composition.

Thymus mastichina, also called mastic thyme or Spanish marjoram, is endemic to the Iberian Peninsula, where it is widely used in folk medicine especially for treating digestive and respiratory systems disorders, and as a condiment to season olives. This work describes for the first time the detailed phenolic composition of exhaustive hydroethanolic extracts and aqueous decoctions of Thymus mastichina. Unlike other species of the Thymus genera, Thymus mastichina extracts contain high amounts of salvianolic acid derivatives, with salvianolic acid A isomer being the main derivative. This isomer was identified in extracts from Thymus mastichina for the first time. Also, an undescribed salvianolic acid derivative in Thymus mastichina was identified and its structure was tentatively described. Extracts from Thymus mastichina showed significant scavenging activity of 2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) radical cation, hydroxyl, and nitric oxide radicals. The anti-proliferative effect of both T. mastichina extracts were tested against Caco-2 and HepG2 cells; the hydroethanolic extract showed a high anti-proliferative activity against Caco-2 cells compared to HepG2 cells (at 24 h exposure, the concentration that inhibits 50% of proliferation, IC50, was 71.18 ± 1.05 µg/mL and 264.60 ± 11.78 µg/mL for Caco-2 and HepG2, respectively). Thus, these results make this species a promising candidate for further investigation of its anti-tumoral potential. Therefore, Thymus mastichina can be potentially used as a functional food (used as a decoction or herbal tea) or as a source of bioactive ingredients with antioxidant and anti-proliferative properties.

Purification of antioxidant peptides of Moringa oleifera seeds and their protective effects on H2O2 oxidative damaged Chang liver cells

Eight novel and three known antioxidant peptides isolated from protein hydrolysate of Moringa oleifera seeds, using ultrafiltration, anion-exchange chromatography, gel filtration chromatography and reversed phase high performance liquid chromatography (RP-HPLC). The novel peptides were identified as Gly-Tyr (GY), Pro-Phe-Glu (PFE), Tyr-Thr-Arg (YTR), Phe-Gly (FG), Gln-Tyr (QY), Ile-Asn (IN), Ser-Phe (SF), Ser-Pro (SP), and the known peptides were identified as Tyr-Phe-Glu (YFE), Ile-Tyr (IY) and Leu-Tyr (LY), respectively, using protein amino acid sequence analyzer and electrospray ionization-mass spectrometry. All the eleven peptides exhibited strong scavenging activities on 2,2-Diphenyl-1picrylhydrazyl radical (DPPH) (EC50 2.28, 1.60, 1.77, 2.15, 0.97, 1.30, 0.75, 0.91, 1.21, 0.79, and 1.37 mg/L, respectively) and 2,2-azino-bis (3-ethylbenzothia zoline-6-sulfonic acid) diammonium salt radical (ABTS+) (EC50 1.03, 0.84, 0.95, 0.65, 0.37, 0.54, 0.33, 0.36, 0.67, 0.32 and 0.38 mg/mL, respectively). In addition, SF and QY showed protective effects on oxidative damage Chang liver cells induced by H2O2, and the contents of aspartate aminotransferase (ALT), alanine aminotransferase (AST) and malondialdehyde (MDA) decreased with the increasing concentrations of SF and QY. Furthermore, SF and QY could significantly increase the levels of superoxide dismutase (SOD) and catalase (CAT), thereby effectively scavenge reactive oxygen species (ROS) in H2O2-induced oxidative damaged Chang liver cells (P < 0.05). These results suggested that SF and QY had the ability to protect Chang liver cells from oxidative stress damage and might serve as potential antioxidants or oxidative damage cytoprotective agents used in pharmaceutical and health food industries.

Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions.

Rational control of the molecular arrangement in solids has been the subject of intense research for many years. In particular, the structural control of bis(ethylenedithio)tetrathiafulvalene (ET) radical cations has attracted special interest because of the primary effect on the electronic properties of the salts. In this study, we obtained the first ET cation radical salts formed with nonuniform silver(I) complex polyanions, which involve multiple kinds of openings in the anionic layer, by an electrocrystallization method. θ-(ET)2Ag2(CN)[N(CN)2]2 (1) with a θ-type ET packing motif contains double helical chains composed of AgN(CN)2, whereas α″-(ET)2Ag2(CN)(SCN)2 (2) with an α″-type ET packing motif contains zigzag ladders composed of AgSCN. Both silver(I)-based tube-like assemblies are connected to each other by a cyano group, affording nonuniform polyanionic structures. Although both salts show semiconducting behavior, there is a distinct difference in their spin geometry, with an S = 1/2 Heisenberg antiferromagnetic square lattice in 1, which is associated with charge disproportionation or dynamical charge fluctuation in the ET layers, and an S = 1/2 Heisenberg anisotropic triangular lattice in 2, which results in spin frustration in the ET layers. The ability of the nonuniform polymeric structures in the anionic layers to act as templates for various arrangements of ET radical cations is demonstrated.

Tunable Reduction of 2,4,6-Tri(4-pyridyl)-1,3,5-Triazine: From Radical Anion to Diradical Dianion to Radical Metal-Organic Framework.

The reduction of 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT) with alkali metals resulted in four radical anion salts (1, 2, 4 and 5) and one diradical dianion salt (3). Single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy reveal that 1 contains the monoradical anion TPT.- stacked in one-dimensional (1D) with K+ (18c6) and 2 can be viewed as a 1D magnetic chain of TPT.- , while 4 and 5 form radical metal-organic frameworks (RMOFs). 1D pore passages, with a diameter of 6.0 Å, containing solvent molecules were observed in 5. Variable-temperature EPR measurements show that 3 has an open-shell singlet ground state that can be excited to a triplet state, consistent with theoretical calculation. The work suggests that the direct reduction approach could lead to the formation of RMOFs.

Tunable Reduction of 2,4,6‐Tri(4‐pyridyl)‐1,3,5‐Triazine: From Radical Anion to Diradical Dianion to Radical Metal–Organic Framework

AbstractThe reduction of 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (TPT) with alkali metals resulted in four radical anion salts (1, 2, 4 and 5) and one diradical dianion salt (3). Single‐crystal X‐ray diffraction and electron paramagnetic resonance (EPR) spectroscopy reveal that 1 contains the monoradical anion TPT.− stacked in one‐dimensional (1D) with K+(18c6) and 2 can be viewed as a 1D magnetic chain of TPT.−, while 4 and 5 form radical metal‐organic frameworks (RMOFs). 1D pore passages, with a diameter of 6.0 Å, containing solvent molecules were observed in 5. Variable‐temperature EPR measurements show that 3 has an open‐shell singlet ground state that can be excited to a triplet state, consistent with theoretical calculation. The work suggests that the direct reduction approach could lead to the formation of RMOFs.

Effects of halogen atom replacement on the structure and magnetic properties of a molecular crystal with supramolecular two-dimensional network mediated via sulfur’s σ-holes

We prepared a novel Pt(mnt)2 (mnt = maleonitriledithiolato) anion radical salt (ethyl-4-iodothiazolium)2[Pt(mnt)2]3 (Pt-I) and investigated the structure and magnetic properties. The chemical composition indicated the existence of two negative charges (electrons) on three Pt(mnt)2 anions. The crystal structure of Pt-I contained a supramolecular rhombic motif mediated via sulfur’s σ-holes on the cation. The anions and cations formed a two-dimensional (2D) supramolecular network via noncovalent cation···anion interactions, where the arrangement of the ions was similar to that of an analogous complex (ethyl-4-bromothiazolium)2[Pt(mnt)2]3 (Pt-Br). On the other hand, the orientation of the cations and the stacking manner of the anions along the direction perpendicular to the 2D supramolecular network were different in Pt-I and Pt-Br. Such structural differences are attributed to the strength of the halogen bond, which is greater in iodine than in bromine. The comparison of the crystal structures between Pt-Br and Pt-I allowed us to estimate the contribution of the noncovalent interactions to the parent crystal structure. The magnetic investigations revealed the strong antiferromagnetic interaction (J/kB = −571 K for T > 280 K) between the spins on the trimerized anion. The interaction was greater in Pt-I than in Pt-Br, reflecting the stronger trimerization in Pt-I. These results suggest that sulfur-mediated chalcogen bonds can be robust enough to dominate the primary arrangement of molecules and the resulted physical properties, even in the presence of the other noncovalent intermolecular interactions or even upon the atomic replacements. Sulfur-based chalcogen bonds would be effective to realize desired structures and properties in molecular materials, while understanding the hierarchy of the noncovalent interactions operated in the crystal would be important for the precise crystal engineering.

Tricoordinate Nontrigonal Pnictogen‐Centered Radical Anions: Isolation, Characterization, and Reactivity

AbstractThe search for main‐group element‐based radicals is one of the main research topics in contemporary chemistry because of their fascinating chemical and physical properties. The Group 15 element‐centered radicals mainly feature a V‐shaped two coordinate structure, with a couple of radical cations featuring trigonal tricoordinated geometry. Now, nontrigonal compounds R3E (E=P, As, Sb) were successfully synthesized by introducing a new rigid tris‐amide ligand. The selective one‐electron reduction of R3E afforded the first stable tricoordinate pnictogen‐centered radical anion salts; the pnictogen atoms retain planar T‐shaped structures. EPR spectroscopy and calculations reveal that the spin density mainly resides at the p orbitals of the pnictogen atoms, which is perpendicular to the N3E planes.