Preparation, structure, reactivity, Lewis acidic and fluorescence properties of arylpyridine based boron C,N‐chelates featuring weakly coordinating anions. DOI
Karel Škoch,

Michaela Buziková,

Dráhomír Hnyk

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 7, 2024

Abstract Herein, we present the preparation of a series electronically and/or sterically distinct borenium‐type species based on simple 2‐arylpyridine scaffold. Corresponding arylpyridine was firstly subjected to electrophilic borylation (BBr 3 / i‐ Pr 2 NEt) and formed BBr chelate reduced with LiAlH 4 yield boron dihydride. Elimination one hydride led Lewis acidic borenium‐like products. Four methods elimination were evaluated influence counterions reactivity, luminescent properties assessed both experimentally computationally. Arylpyridine chelates featuring weakly coordinating exhibit fluorescent upon UV irradiation. Several general trends inferred modulate emission wavelength fluorescence quantum yield. Based our observations, have devised prepared fluorophores yellow‐green yields up 93 %.

Language: Английский

Exploring and leveraging aggregation effects on reactive oxygen species generation in photodynamic therapy DOI Creative Commons

Zeyan Zhuang,

Jianqing Li,

Pingchuan Shen

et al.

Aggregate, Journal Year: 2024, Volume and Issue: 5(4)

Published: March 10, 2024

Abstract Aggregate‐level photodynamic therapy (PDT) has attracted significant interest and driven substantial advances in multifunction phototheranostic platforms. As exemplified by two typical instances of aggregation‐caused quenching reactive oxygen species (ROS) aggregation‐induced generation ROS, the aggregation effect plays a role on ROS photosensitizers (PSs), which is worthy in‐depth exploration full utilization. However, contrast to well‐developed researches luminescence, studies concerning are currently relatively nascent disjointed stage, lacking guidance from firmly established research paradigm. To advance this regard, review aims at providing consolidated overview fundamental principles status effects generation. Here, can be organized into main facets. One involves comparison between isolated state aggregated state, mainly conducted methods changing solvent environments adding adjuvants given solvent. The other underscores distinctions different aggregate states, consisting three parts, namely within same or categories based classification single‐component multicomponent aggregates. In endeavor, we will present our views current methodologies that explore how affects highlight design strategies leverage optimize PS regiments. We aspire propel advancement platforms accelerate clinical implementation precision medicine, inspire more contributions aggregate‐level photophysics photochemistry, pushing science materials forward.

Language: Английский

Citations

38
Ligand Exchange at Carbon: Synthetic Entry to Elusive Species and Versatile Reagents DOI Creative Commons
Felix Krischer, Viktoria H. Gessner

JACS Au, Journal Year: 2024, Volume and Issue: 4(5), P. 1709 - 1722

Published: April 15, 2024

How different is carbon compared to other elements in the periodic table? Can compounds be regarded as coordination complexes with central element undergoing a facile exchange of its ligands? Although clearly plays special role among table, recent studies have drawn parallels between bonding situation and reactivity transition metal complexes. This Perspective summarizes reports about ylidic zwitterionic that were shown exhibit ambiguous situations can interpreted donor–acceptor interactions similar bond neutral ligand. Based on this conception, ligand reactions prototypical realized at atoms, enabling new synthetic strategies for synthesis reactive species building blocks. In particular, N2, CO, phosphine ligands led development mild method accessing reagents unusual properties, such vinylidene ketenes or stable ketenyl anions, open up diverse but still poorly explored follow-up chemistry.

Language: Английский

Citations

12
Access to Bis-Silylene-Stabilized Group 13 Cations DOI
Moushakhi Ghosh, Prakash Panwaria, Srinu Tothadi

et al.

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

Published: Jan. 6, 2025

Herein, we report the isolation of pyridine moiety-functionalized SiNSi pincer-based bis-silylene ligand (1) and its reactivity toward various halide precursors (X = Br I) group 13 elements (M Al, Ga, In). This gave us straightforward access to pincer-coordinated cations (2–7). These complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear magnetic resonance spectroscopy (1H, 13C, 29Si), high-resolution mass spectrometry techniques. Their electronic properties were further analyzed with help quantum chemical calculations.

Language: Английский

Citations

1
Lewis Superacidic Heavy Pnictaalkene Cations: Comparative Assessment of Carbodicarbene-Stibenium and Carbodicarbene-Bismuthenium Ions DOI
Levi S. Warring, Jacob E. Walley, Diane A. Dickie

et al.

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(46), P. 18640 - 18652

Published: Nov. 9, 2022

We report a comprehensive assessment of Lewis acidity for series carbone-stibenium and -bismuthenium ions using the Gutmann-Beckett (GB) method. These new antimony bismuth cations have been synthesized by halide abstractions from (CDC)PnBr3 [(pyCDC)PnBr2][Br] (CDC = carbodicarbene; Pn Sb or Bi; py pyridyl). The reaction (CDC)SbBr3 (1) with one two equivalents AgNTf2 (NTf2 bis(trifluoromethanesulfonyl)imide) AgSbF6 gives stibaalkene mono- dications form [(CDC)SbBr3-n][A]n (2-4; n 1,2; A NTf2 SbF6). trication [(CDC)2Sb][NTf2]3 (5) was also isolated collectively these molecules fill gap among cationic pnictaalkenes. are compared to related CDC-bismaalkene complexes 6-9. With goal preparing highly acidic compounds, tridentate bis(pyridine)carbodicarbene (pyCDC) used as ligand access (10, 12) trications [(pyCDC)Pn][NTf2]3 (Pn (11), Bi (13)), forgoing need second CDC in synthesis 5. bonding situation is elucidated through electron density energy decomposition analyses combination natural orbital chemical valence theory. In each complex, there exists CDC-Pn double interaction, consisting strong σ-bond weaker π-bond, whereby π-bond gradually strengthens increase charge complex. Notably, [(CDC)SbBr][NTf2]2 (4) has an acceptor number (AN) (84) that comparable quintessential acids such BF3, tricationic pnictaalkene 11 13 exhibit ANs 109 Sb) 84 Bi), respectively, which highest values reported any cation. Moreover, calculated fluoride ion affinities (FIAs) 99.8 94.3 kcal/mol, larger than SbF5 (85.1 kcal/mol), suggest superacids.

Language: Английский

Citations

36
Air- and photo-stable luminescent carbodicarbene-azaboraacenium ions DOI
Chun‐Lin Deng, D. Akachukwu,

Bi Youan E. Tra

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 16(3), P. 437 - 445

Published: Dec. 5, 2023

Language: Английский

Citations

17
Synthesis, Characterization, and Properties of Three-Dimensional Analogues of 9-Borafluorenes DOI
Chonghe Zhang, Junyi Wang, Zhenyang Lin

et al.

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(45), P. 18275 - 18284

Published: Nov. 4, 2022

Three-dimensional (3D) analogues of 9-borafluorenes, (C2B10H10)2BR (R = Cl (1), Br (2), H (3, merely as ether or silane adduct), phenyl (4), mesityl (5)), were synthesized and fully characterized. Gutmann–Beckett computational fluoride/hydride ion affinity (FIA/HIA) studies confirmed the Lewis superacidity 1–4, with acidity 1–3 being higher than that corresponding 3D 9,10-diboraanthracenes (DBA). The group C4B borole unit are nearly coplanar in solid state, while rotation 5 is hindered, forcing to adopt a large C4B/Mes dihedral angle, which leads distinct properties: air-stable bluish-violet fluorescence arising from intramolecular charge-transfer (ICT) transition. 29Si NMR spectra indicated high silylium cation character 3·Et3SiH. reaction 4 Ph3CBr yielded (Ph3C)+[(C2B10H10)2B(Ph)Br]− (6). 4/PPh3 pair was capable splitting dihydrogen Si–H bond triethylsilane.

Language: Английский

Citations

21
A Borenium-Borane Composite for Exhaustive Reduction of Oxo-Chemicals DOI Creative Commons
Xinying Li, Kai Wang, Ye Li

et al.

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

Published: Jan. 2, 2025

Borenium ions have attracted significant attention in organic transformations due to their strong Lewis acidity. The reported borenium are often stabilized by sterically demanding substituents and coordination bonds. Herein, we synthesized a small steric borenium-equivalent NH3BH2OTf subjected it the exhaustive reduction of carboxylic functional group methyl group, which shows broad tolerance. This system can also undergo reductive deoxygenation reaction alcohols, ethers, other oxo-chemicals (>100 examples). mechanistic studies revealed that situ-generated NH3BH2OTf/[NH3BH2(sol)]OTf, rendering borenium-like properties, plays crucial role these interacting with O atom substrates activate carbonyl facilitating cleavage C–O bond. work has not only offered for but is great significance providing insight into application various reactions.

Language: Английский

Citations

0
Dicationic 1-Germa and 1-Stannavinylidenes: Synthesis, Structure, and Reactivity DOI Creative Commons
Yuankai Li, Mu Huan, Zhuchunguang Liu

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(3), P. 1289 - 1298

Published: Feb. 19, 2025

The synthesis of heteronuclear vinylidene analogues containing heavier group 14 elements (R2C═E:, E = Si, Ge, Sn) has been a challenging task due to their inherent instability. In this study, we report the dicationic 1-germavinylidene (3Ge) and 1-stannavinylidene (3Sn) by using sym-bis(2-pyridyl)-tetraphenylcarbodiphosphorane (CDPPy2) as donor ligand. Both 3Ge 3Sn have characterized single-crystal X-ray diffraction analysis, NMR spectroscopy, high-resolution mass spectrometry. structural supported results theoretical calculations, confirms that feature polarized C═E double bond lone pair electrons located at atom (E Ge Sn). reactions with IDippMCl (M Cu, Ag, Au) give M–Cl addition products. Mechanistic studies on activation Au–Cl demonstrate its ambiphilicity. This work represents an example utilization carbone ligand both σ π for analogues.

Language: Английский

Citations

0
Synthesis and Reactivity of an Anionic Diazoolefin DOI Creative Commons
Bastiaan Kooij, Zhaowen Dong, Farzaneh Fadaei‐Tirani

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: June 30, 2023

Abstract Bent (hetero)allenes such as carbodicarbenes and carbodiphosphoranes can act neutral C‐donor ligands, diverse applications in coordination chemistry have been reported. N‐Heterocyclic diazoolefins are heterocumulenes, which function a similar fashion L‐type ligands. Herein, we describe the synthesis reactivity of an anionic diazoolefin. This compound displays distinct compared to diazoolefins, evidenced by preparation diazo compounds via protonation, alkylation, or silylation. The diazoolefin be employed ambidentate, X‐type ligand salt metathesis reactions with metal halide complexes. Extrusion dinitrogen was observed reaction PCl(N i Pr 2 ) , resulting stable phosphinocarbene.

Language: Английский

Citations

9
The emergence of zerovalent carbon compounds from structural curiosities to organocatalysts DOI Creative Commons
Allegra L. Liberman‐Martin

Cell Reports Physical Science, Journal Year: 2023, Volume and Issue: 4(8), P. 101519 - 101519

Published: July 31, 2023

Low-valent main group compounds have reactivity patterns and properties reminiscent of transition metals. While divalent carbon such as carbenes are widely studied ligands organocatalysts, zerovalent species received considerably less attention. This perspective highlights the compounds, focusing on their first applications organocatalysts for small molecule reduction polymerization reactions.

Language: Английский

Citations

9