Selective Activation of Chalcogen Bonding: An Efficient Structuring Tool toward Crystal Engineering Strategies

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(3), P. 362 - 374

Published: Jan. 26, 2024

ConspectusAmong the noncovalent interactions available in toolbox of crystal engineering, chalcogen bonding (ChB) has recently entered growing family σ-hole interactions, following strong developments based on halogen (XB) interaction over last 30 years. The monovalent character halogens provides directionality and strength. Combined with extensive organic chemistry Br I derivatives, it led to many applications XB, solution (organo-catalysis, anion recognition transport), solid state (cocrystals, conducting materials, fluorescent topochemical reactions, ...), soft matter (liquid crystals, gels,···), biochemistry. presence two σ-holes divalent chalcogens ability activate them, as electron-withdrawing groups (EWG) fueled more recent interest bonding. However, despite being identified for years, ChB still struggles make a mark due (i) underdeveloped synthetic heavier Se Te; (ii) limited stability chalcogenides, especially tellurides; (iii) poor predictability associated σ-holes. It therefore invites great deal attention molecular chemists design develop selected donors, scrutiny fundamentals their successful use different applications. This Account aims summarize our own contributions this direction that extend from fundamental studies focused addressing lack directionality/predictability systematic demonstration its potential, specifically particularly toward anionic networks one hand, reactions other hand.In Account, we share results aimed at recovering same degree strength found by focusing Te systems substituents, them an EWG, strongly unbalance both For purpose, explored dissymmetrization concept within three chemical families, selenocyanates R–SeCN, alkynyl derivatives R–C≡C–(Se/Te)Me, o-carborane derivatives. Such compounds were systematically engaged cocrystals either halides or neutral bipyridines acceptors, revealing potential chelate well organize reactive molecules such alkenes butadiynes [2+2] cycloadditions polydiacetylene formation, respectively. selective activation is not but can be effectively used all (pnictogen bond, tetrel etc.) where needs control interaction.

Language: Английский

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Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to P^III‐Stereogenic Compounds

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 26, 2024

Intermolecular pnictogen bonding (PnB) catalysis has received increased interest in non-covalent organocatalysis. It been demonstrated that organic electron-deficient atoms can act as prospective Lewis acids. Here, we present a catalytic approach for the asymmetric synthesis of chiral P

Language: Английский

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Selectivity in Adduct Formation of a Bidentate Boron Lewis Acid

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(27)

Published: Feb. 29, 2024

Abstract A bidentate boron Lewis acid based on 1,8‐diethynylanthracene has been studied in detail with respect to its adduct formation diamines and diphosphanes of different linker lengths between the donor functions. clear correlation length bifunctional base 1 : adducts, 2 adducts or oligomers was found. The were characterized solution by NMR titration experiments structurally X‐ray diffraction. In addition, competition host system ZR 3 (Z=N, P; R=H, Me) demonstrated generally higher stability alkylphosphane compared alkylamine results provide a general insight into acids guests sizes as well differences borane‐amine borane‐phosphane adducts.

Language: Английский

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A Geminal Antimony(III)/Phosphorus(III) Frustrated Lewis Pair

Chemical Science, Journal Year: 2024, Volume and Issue: 15(30), P. 12118 - 12125

Published: Jan. 1, 2024

(F 5 C 2 ) SbCH P( t Bu) reacts in a FLP-like manner with CS , SO PhNCO/S and (MePh P)AuCl. The AuCl adduct show secondary interactions between the Lewis acidic Sb atom electron rich atoms, intra- intermolecular, respectively.

Language: Английский

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Poly-pnictogen bonding: trapping halide ions by a tetradentate antimony(iii) Lewis acid

Chemical Science, Journal Year: 2023, Volume and Issue: 14(46), P. 13551 - 13559

Published: Jan. 1, 2023

A tetradentate host system with four CC–Sb(C 2 F 5 ) functions binds halide ions in a distorted square planar coordination. Experimental and calculated structures reveal complex interplay of attractive pnictogen bonding Coulomb repulsion.

Language: Английский

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Pnictogen Bond-Mediated Coassemblies for Noncovalent Molecular Glass

Nano Letters, Journal Year: 2025, Volume and Issue: 25(2), P. 905 - 913

Published: Jan. 7, 2025

Pnictogen bond (PnB) occurring on the group-15 elements is recognized as σ- or π-hole-based interaction that has garnered attention in fields of anion recognition and organocatalysis. Due to polyvalent feature pnictogens high directionality, PnB possesses potential design convergent coassembled materials with acceptors containing lone pair electrons anions, which however rarely explored so far. Herein, we unveil role antimony (Sb)-based donors producing self-assembled chiroptical electron acceptors. Steric effect electronic properties determined exposure strength σ-holes direct complexation between components. leads profound property self-assembly behavior evolutions compared pristine assembly, including crystallinity, photophysical, morphological, properties. The complexes exhibited an accelerated photoisomerization. Ascribed multiple Sb donors, amorphous structures were generated, enabling formation glassy materials.

Language: Английский

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Intramolecular Interactions between the Pnictogen Groups in a Rigid Ferrocene Phosphinostibine and the Corresponding Phosphine Chalcogenides, Stiboranes, and Their Complexes

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

Published: May 25, 2025

Differences in the chemical properties of phosphorus and antimony enable synthesis heteroditopic derivatives whose can be modified by altering pnictogen substituents. In this work, 1-(diphenylstibino)-2-(dicyclohexylphosphino)ferrocene, [Fe(η5-1-Ph2Sb-2-Cy2PC5H3)(η5-C5H5)] (1), corresponding phosphine chalcogenides [Fe(η5-1-Ph2Sb-2-Cy2P(E)C5H3)(η5-C5H5)] (E = O, S, Se) catecholatostiboranes [Fe(η5-1-Ph2(Cl4C6O2)Sb-2-Cy2P(E)C5H3)(η5-C5H5)] void, were examined, with a focus on intramolecular donor-acceptor interactions between Experimental data theoretical analysis consistently indicated that these described as bonding Lewis acidic lone pair at substituent (either or chalcogen atom) they are significantly stronger stiboranes due to increased acidity Sb atom. Noncovalent also observed chlorogold(I) complexes obtained from 1 catecholatostiborane [Fe(η5-1-Ph2(Cl4C6O2)Sb-2-Cy2PC5H3)(η5-C5H5)] P-donors. As shown experiments Au-mediated cyclization N-propargylbenzamide, noncoordinated group influenced catalytic Au(I) complexes. Notably, an Cl → bond affected molecular geometry Pd(II) complex [PdCl2(1-κ2P,Sb)], which turn suggested structural influence exerted ligands type needs assessed care.

Language: Английский

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Tridentate Lewis Acids Based on Tribenzotriquinacene Chalices

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(39)

Published: May 14, 2024

Chalice-shaped tridentate poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Stannylation of alkyne units, attached via phenyl-spacers to benzhydrylic positions TBTQ scaffold, with Me

Language: Английский

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Oxidation-dependent Lewis acidity in chalcogen adducts of Sb/P frustrated Lewis pairs

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(28), P. 11762 - 11768

Published: Jan. 1, 2024

The reactions of the frustrated Lewis pair (F

Language: Английский

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Computational Insight into the Nature and Strength of the π-Hole Type Chalcogen∙∙∙Chalcogen Interactions in the XO2∙∙∙CH3YCH3 Complexes (X = S, Se, Te; Y = O, S, Se, Te)

International Journal of Molecular Sciences, Journal Year: 2023, Volume and Issue: 24(22), P. 16193 - 16193

Published: Nov. 10, 2023

In recent years, the non-covalent interactions between chalcogen centers have aroused substantial research interest because of their potential applications in organocatalysis, materials science, drug design, biological systems, crystal engineering, and molecular recognition. However, studies on π-hole-type chalcogen∙∙∙chalcogen are scarcely reported literature. Herein, intermolecular model complexes formed XO2 (X = S, Se, Te) CH3YCH3 (Y O, were systematically studied by using quantum chemical computations. The stabilized via one primary X∙∙∙Y bond (ChB) secondary C-H∙∙∙O hydrogen bonds. binding energies range -21.6~-60.4 kJ/mol. distances significantly smaller than sum van der Waals radii corresponding two atoms. ChBs all except for SO2∙∙∙CH3OCH3 complex strong strength display a partial covalent character revealed conducting theory atoms molecules (QTAIM), interaction plot (NCIplot), natural orbital (NBO) analyses. symmetry-adapted perturbation (SAPT) analysis discloses that primarily dominated electrostatic component.

Language: Английский

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