Atomically Dispersed p‐Block Aluminum‐Based Catalysts for Oxygen Reduction Reaction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 13, 2024

The main group metals are commonly perceived as catalytically inert in the context of oxygen reduction reactions (ORR) due to delocalized valence orbitals. Regulating local environment and structure metal center coordinated by nitrogen ligands (M-N

Language: Английский

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Ambient Temperature Isolation of a Monatomic Boron(0) Complex

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

The first bottleable example of a neutral Group 13 atom bound only by donor ligands (L) has been fully characterized spectroscopic methods and its structure determined single-crystal X-ray diffraction study. A two-coordinate paramagnetic L2B0 complex can readily be accessed through facile reduction reaction is stabilized π-accepting cyclic (alkyl)(amino)carbene (CAAC) ligands. Further (CAAC)2B leads to the isolation stable diamagnetic boride anion. In turn, oxidation putative formation transient cationic borylene, which trapped form boron(I) complex. Density functional theory calculations support formulation as boron(0) strong multiple bonding.

Language: Английский

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Synthesis of medium-sized benzo[b]azocines and benzo[b]azonines by photoinduced 8-/9-endo sulfonyl-cyclization

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(8), P. 2309 - 2316

Published: July 24, 2023

Language: Английский

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Diradical B/N‐Doped Polycyclic Hydrocarbons

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(9)

Published: Jan. 5, 2023

Heterocyclic diradicaloids with atom-precise control over open-shell nature are promising materials for organic electronics and spintronics. Herein, we disclose quinoidal π-extension of a B/N-heterocycle generating B/N-type diradicaloids. Two π-extended B/N-doped polycyclic hydrocarbons that feature fusion the motif antiaromatic s-indacene or dicyclopenta[b,g]naphthalene core were synthesized. This leads to their electronic nature, which stands in contrast multiple-resonance effect conventional emitters. These have modulated (anti)aromaticity enhanced diradical characters comparing all-carbon analogues, as well intriguing properties, such magnetic activities, narrow energy gaps highly red-shifted absorptions. study thus opens new space both π-systems heterocyclic

Language: Английский

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Monosubstituted Doublet Sn(I) Radical Featuring Substantial Unquenched Orbital Angular Momentum

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6914 - 6920

Published: March 16, 2023

Due to their intrinsic high reactivity, isolation of heavier analogues carbynes remains a great challenge. Here, we report the synthesis and characterization neutral monosubstituted Sn(I) radical (2) supported by sterically hindered hydrindacene ligand, which represents first tin analogue free carbyne. Different from all Sn(I/III) species reported thus far, presence sole Sn-C σ bond in 2 renders remaining two Sn 5p orbitals energetically almost degenerate, one is singly occupied other empty. Consequently, its S = 1/2 ground state possesses two-fold orbital pseudo-degeneracy substantial unquenched angular momentum, as evidenced component g matrix (1.957, 1.896, 1.578) being considerably less than 2. Consistent with this unique electronic structure, can bind an N-heterocyclic carbene afford two-coordinate initiate one-electron transfer benzophenone furnish Sn(II)-ketyl anion adduct. As manifestation Sn-centered nature, reacts diphenyl diselenide p-benzoquinone form Sn-S Sn-O bonds, respectively.

Language: Английский

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Rodlike nanomaterials from organic diradicaloid with high photothermal conversion capability for tumor treatment

Aggregate, Journal Year: 2023, Volume and Issue: 4(5)

Published: May 25, 2023

Abstract Organic diradicaloids with unique open‐shell structures and properties have been widely used in organic electronics spintronics. However, their advantageous optical explored less the biomedical field. In this work, photothermal conversion behaviors of a boron‐containing diradicaloid (BOD) are reported. BOD can assemble 1,2‐distearoyl‐sn‐glycero‐3‐phosphoethanolamine‐poly(ethylene glycol) to form rodlike nanoparticles (BOD NPs). These as‐prepared NPs exhibit high capability robust stability. Notably, they possess morphological superiority, which guarantees effective therapy tumors. This work thus demonstrates promise as efficient agents for applications.

Language: Английский

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An Isolable One‐Coordinate Lead(I) Radical with Strong g‐Factor Anisotropy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 5, 2024

Abstract Lead‐based radicals in the oxidation state of +1 are elusive species and highly challenging to isolate condensed phase. In this study, we present synthesis characterization first isolable free plumbylyne radical 2 bearing a one‐coordinate Pb(I) atom. It reacts with an N ‐heterocyclic carbene (NHC) afford two‐coordinate NHC‐ligated 3 . represent Pb(I)‐based radicals. Theoretical calculations electron paramagnetic resonance analysis revealed that unpaired mainly resides at Pb 6p orbital both Owing unique nature atom , it possesses two‐fold pseudo‐degeneracy substantial unquenched angular momentum, exhibits hitherto strongest g ‐factor anisotropy ( x,y,z =1.496, 1.166, 0.683) amongst main group Preliminary investigations into reactivity unveiled its Pb‐centered nature, plumbylenes were isolated as products.

Language: Английский

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Polycationic Open‐Shell Cyclophanes: Synthesis of Electron‐Rich Chiral Macrocycles, and Redox‐Dependent Electronic States

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: Feb. 27, 2024

π-Conjugated chiral nanorings with intriguing electronic structures and chiroptical properties have attracted considerable interests in synthetic chemistry materials science. We present the design principles to access new macrocycles (1 2) that are essentially built on key components of main-group electron-donating carbazolyl moieties or π-expanded aza[7]helicenes. Both show unique molecular conformations a (quasi) figure-of-eight topology as result conjugation patterns 2,2',7,7'-spirobifluorenyl 1 triarylamine-coupled aza[7]helicene-based building blocks 2. This nature redox-active, carbazole-rich backbones enabled these be readily oxidized chemically electrochemically, leading sequential production series positively charged polycationic open-shell cyclophanes. Their redox-dependent states resulting multispin polyradicals been characterized by VT-ESR, UV/Vis-NIR absorption spectroelectrochemical measurements. The singlet (ΔE

Language: Английский

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Isolation and Reactivity of Carbene-Stabilized Carbon Disulfide Radical Anions

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

The reaction of CAAC-CS2 betaine (1; CAAC = cyclic(alkyl)(amino)carbene) and alkali metal reductants under ambient conditions yields carbene-stabilized carbon disulfide radical anions as crystalline salts. radicals 3–5 form multinuclear clusters featuring diverse sulfide interactions, which promote unusual reductive coupling cyclization adjacent CS2 units to C2S3 heterocycles (6). addition crown ethers sequesters the cations facilitates cleavage yield stable [CAAC-CS2]·– monomers (7 8). Calculated natural atomic spin populations suggest that densities in clustered monomeric species are comparable evenly distributed between subunits. Subsequent reductions afford [CAAC-CS2]2– dianions (9–12), can be reoxidized by comproportionation reactions with 1. are, turn, oxidized 1 through salt elimination transition metals. Cyclic voltammograms feature reversible 1/1·–/12– couples a small separation events (ΔΔG 11.1 kcal mol–1). All isolated compounds were characterized combination electron paramagnetic resonance spectroscopy, heteronuclear NMR infrared single-crystal X-ray diffraction. Insights into their electronic structure supported density functional theory calculations.

Language: Английский

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A Dynamic Triradical: Synthesis, Crystal Structure, and Spin Frustration

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17292 - 17298

Published: July 26, 2023

Polyradicals, i.e., multispin organic molecules, are playing important roles in radical-based material applications for their spin–spin interaction. A dynamic covalently bonded molecule may endow materials with added function such as memory and switching. However, a species has yet to be reported. We here report the synthesis, characterization, crystal structure of triradical species. It is generated by self-assembly two molecules through Lewis acid coupled electron transfer. The crystalline spin-frustrated without Jahn–Teller distortion at low temperature, while it dissociates back diamagnetic starting solution high temperature. reversible process tracked variable-temperature NMR, EPR, UV–vis–NIR spectroscopy. Isolation, property study, bonding investigation on lay foundation design functional polyradicals potential application or switching devices.

Language: Английский

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