Bis-[cyclic(alkyl)(amino)carbene]-derived diradicals.

Crystalline polymeric structures of trans-1,4-cyclohexylene bridged N-tethered bis-CAACs in the form of their LiOTf adducts were synthesized and isolated. These were further used as building blocks for the synthesis of crystalline (amino)(carboxy)-based diradicals. The triplet diradical character of these compounds was unambiguously confirmed by the presence of a half-field signal in their EPR spectra. Theoretical calculations show that the singlet state is marginally more stable than the triplet state.

Field-induced bound-state condensation and spin-nematic phase in SrCu2(BO3)2 revealed by neutron scattering up to 25.9 T.

In quantum magnetic materials, ordered phases induced by an applied magnetic field can be described as the Bose-Einstein condensation (BEC) of magnon excitations. In the strongly frustrated system SrCu2(BO3)2, no clear magnon BEC could be observed, pointing to an alternative mechanism, but the high fields required to probe this physics have remained a barrier to detailed investigation. Here we exploit the first purpose-built high-field neutron scattering facility to measure the spin excitations of SrCu2(BO3)2 up to 25.9 T and use cylinder matrix-product-states (MPS) calculations to reproduce the experimental spectra with high accuracy. Multiple unconventional features point to a condensation of S = 2 bound states into a spin-nematic phase, including the gradients of the one-magnon branches and the persistence of a one-magnon spin gap. This gap reflects a direct analogy with superconductivity, suggesting that the spin-nematic phase in SrCu2(BO3)2 is best understood as a condensate of bosonic Cooper pairs.

Reduction of 2-H-substituted pyrrolinium cations: the carbon-carbon single bond in air stable 2,2'-bipyrrolidines as a two-electron-source.

Reduction of 2-H-substituted pyrrolinium cations via initially formed secondary radicals results in either dimerisation or H-abstracted products, while the outcome depends on the N-substituents. The resultant central carbon-carbon single bond in the dimerised 2,2'-bipyrrolidine derivatives can be oxidised chemically and electrochemically. The notably air and moisture-stable dimers were subsequently utilised as a source of two electrons in various chemical transformations.

Air and Moisture Stable para- and ortho-Quinodimethane Derivatives Derived from bis-N-Heterocyclic Olefins.

Herein we report the development of a new methodology for the synthesis of various quinodimethane derivatives under two-electron oxidation of bis-N-heterocyclic olefins linked by different π-conjugated aromatic spacers. In case of para- and ortho-phenylene bridge, we obtained air and moisture stable diimidazolium para- and ortho-quinodimethane derivatives. Analogues of the para-phenylene spacer such as tetrafluoro-p-phenylene and p-anthracene also led to the corresponding air and moisture stable quinodimethane derivatives. This emphasizes the influence of imidazolium substituents which facilitate the air and moisture stability of the quinodimethane derivatives. Differences were observed for the electron transfer processes: two one-electron vs one two-electron redox transitions between bis-N-heterocyclic olefins and diimidazolium-quinodimethanes depending on the employed π-conjugated aromatic spacer. The formation of the π-conjugated radical-cations, transient redox intermediates between bis-N-heterocyclic olefins and diimidazolium-quinodimethanes, was addressed by an EPR investigation.

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents.

Herein, a new type of carbodicarbene (CDC) comprising two different classes of carbenes is reported; NHC and CAAC as donor substituents and compare the molecular structure and coordination to Au(I)Cl to those of NHC-only and CAAC-only analogues. The conjugate acids of these three CDCs exhibit notable redox properties. Their reactions with [NO][SbF6 ] were investigated. The reduction of the conjugate acid of CAAC-only based CDC with KC8 results in the formation of hydrogen abstracted/eliminated products, which proceed through a neutral radical intermediate, detected by EPR spectroscopy. In contrast, the reduction of conjugate acids of NHC-only and NHC/CAAC based CDCs led to intermolecular reductive (reversible) carbon-carbon sigma bond formation. The resulting relatively elongated carbon-carbon sigma bonds were found to be readily oxidized. They were, thus, demonstrated to be potent reducing agents, underlining their potential utility as organic electron donors and n-dopants in organic semiconductor molecules.

A bis-NHC-CAAC dimer derived dicationic diradical.

The isolation of carbon-centered diradicals is always challenging due to synthetic difficulties and their limited stability. Herein we report the synthesis of a trans-1,4-cyclohexylene bridged bis-NHC-CAAC dimer derived thermally stable dicationic diradical. The diradical character of this compound was confirmed by EPR spectroscopy. The variable temperature EPR study suggests the singlet state to be marginally more stable than the triplet state (2J = -5.5 cm-1 (ΔE ST = 0.065 kJ mol-1)). The presence of the trans-1,4-cyclohexylene bridge is instrumental for the successful isolation of this dicationic diradical. Notably, in the case of ethylene or propylene bridged bis-NHC-CAAC dimers, the corresponding dicationic diradicals are transient and rearrange to hydrogen abstracted products.

Realizing 1,1-Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin-2-ols as a Source of Cyclic (Alkyl)(Amino)Carbenes.

Herein we report secondary pyrrolidin-2-ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC-CuI -complexes and cyclic thiones when reacted with CuI -salts and elemental sulfur, respectively, under reductive elimination of water from the carbon(IV)-center. This result demonstrates a convenient and facile access to CAAC-based CuI -salts, which are well known catalysts for different organic transformations. It further establishes secondary alcohols to be a viable source of carbenes-realizing after 185 years Dumas' dream who tried to prepare the parent carbene (CH2 ) by 1,1-dehydration of methanol. Addressed is also the reactivity of water towards CAACs, which proceeds through an oxidative addition of the O-H bond to the carbon(II)-center. This emphasizes the ability of carbon-compounds to mimic the reactivity of transition-metal complexes: reversible oxidative addition and reductive elimination of the O-H bond to/from the C(II)/C(IV)-centre.

An Air-Stable Alkene-Derived Organic Radical Cation.

Alkenes are known to undergo oxidation to radical cations and dications. The radical cations are often highly reactive and not stable under air. Herein, we report the synthesis, isolation, characterization, and molecular structure of an alkene-derived radical cation A, which is stable in air both in the solid state and in solution. The access to this compound was facilitated from E-diamino tri-substituted alkene B as a synthon for the synthesis of A through one-electron oxidation. The E-diamino tri-substituted alkene B was synthesized by the two-electron reduction of N,N'-1,2-propylene-bridged bis-2-phenyl-pyrrolinium cation C. Under two-electron oxidation, alkene B transforms back to cation C involving a double carbocation rearrangement.

Correction: Tethered CAAC-CAAC dimers: oxidation to persistent radical cations and bridging-unit dependent reactivity/stability of the dications.

Correction for 'Tethered CAAC-CAAC dimers: oxidation to persistent radical cations and bridging-unit dependent reactivity/stability of the dications' by Mithilesh Kumar Nayak et al., Chem. Commun., 2021, 57, 1210-1213, DOI: 10.1039/D0CC07385G.

Tethered CAAC-CAAC dimers: oxidation to persistent radical cations and bridging-unit dependent reactivity/stability of the dications.

Herein, we report tethered cyclic(alkyl)(amino)carbene (CAAC) dimers in which two CAAC-motifs are connected by an ethylene-, trans-1,2-cyclohexylene- and propylene-spacer through their N-centres. The 1-electron oxidized radical cations are isolable, whereas a significant influence of the bridging unit on the chemical reactivity becomes apparent in and with the 2-electron oxidized products.

Magnetic-Field-Induced Bound States in Spin-1/2 Ladders.

Motivated by the recently observed intriguing mode splittings in a magnetic field with inelastic neutron scattering in the spin ladder compound (C_{5}H_{12}N)_{2}CuBr_{4} (BPCB), we investigate the nature of the spin ladder excitations using a density matrix renormalization group and analytical arguments. Starting from the fully frustrated ladder, for which we derive the low-energy spectrum, we show that bound states are generically present close to k=0 in the dynamical structure factor of spin ladders above H_{c1}, and that they are characterized by a field-independent binding energy and an intensity that grows with H-H_{c1}. These predictions are shown to explain quantitatively the split modes observed in BPCB.

N,N'-Ethylene-Bridged Bis-2-Aryl-Pyrrolinium Cations to E-Diaminoalkenes: Non-Identical Stepwise Reversible Double-Redox Coupled Bond Activation Reactions.

This work presents a stepwise reversible two-electron transfer induced hydrogen shift leading to the conversion of a bis-pyrrolinium cation to an E-diaminoalkene and vice versa. Remarkably, the forward and the reverse reaction, which are both reversible, follow two completely different reaction pathways. Establishing such unprecedented property in this type of processes was possible by developing a novel synthetic route towards the starting dication. All intermediates involved in both the forward and the backward reactions were comprehensively characterized by a combination of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and theoretical methods. The presented synthetic route opens up new possibilities for the generation of multi-pyrrolinium cation scaffold-based organic redox systems, which constitute decidedly sought-after molecules in contemporary chemistry.

Contrasting reactivity of (boryl)(aryl)lithium-amide with electrophiles: N- vs. p-aryl-C-nucleophilic substitution.

Herein we report two different reactivity modes of lithium(aryl)(boryl)amide, 4, when it is reacted with chlorosilanes such as SiCl4 and MeSiHCl2, and chlorophosphine, Ph2PCl. Thus, the reaction of lithium(aryl)(boryl)amide, 4, with MeSiHCl2 leads exclusively to an N-substitution product, 6. On the other hand, the reaction of 4 with SiCl4 and Ph2PCl proceeds completely differently affording exclusively p-aryl-C-substitution products, 5 and 7, respectively.

An Evaluation of Efficacy and Safety of Commonly Prescribed Drugs and Effect of These Drugs on Quality of Sleep in Patients Suffering From Zoster-Associated Pain.

This observational, prospective, single-center study was conducted to evaluate the efficacy and safety of commonly prescribed drugs for zoster-associated pain and their impact on quality of sleep at a tertiary care hospital in western India. Patients ≥18 years of age, newly diagnosed with zoster-associated pain were evaluated on days 0, 7, 14, 30, 60, 90, 120, 150, and 180 or until resolution of pain, whichever was earlier, using the Wong Baker FACES Pain Rating Scale, Neuropathic Pain Scale, and Insomnia Severity Index for intensity of pain, quality of pain, and quality of sleep, respectively. A total of 78 patients (46.0 [16.3] years) completed the study. They received nonsteroidal anti-inflammatory drugs (65), gabapentin (30), amitriptyline (27), and amitriptyline + gabapentin (21) for mean durations of 7.7 (3.0), 89.2 (7.2), 107.6 (46.3), and 104.5 (46) days, respectively. Improvement in the Wong Baker FACES Pain Rating Scale and Neuropathic Pain Scale score was similar among treatment groups except for a greater fall in Wong Baker FACES Pain Rating Scale score at days 7 and 120 and that in deep pain score at day 7 in combination treatment group vs the amitriptyline group. Clinically significant insomnia was detected in 35 patients at baseline and demonstrated progressive and similar improvement among groups. Treatment modification was required in 20 patients. Zoster-associated pain resolved in 69 patients. Nine adverse drug reactions, mostly mild, nonserious, and nonpreventable, were reported. To conclude, drugs commonly used for zoster-associated pain are effective and well tolerated. These have a similar effect on pain and quality of sleep, except for a possible greater effect of combination treatment in the early phase of intense and deep pain.