Polymeric Lead(II) Iodoacetate: Pb···I and I···I Non‐Covalent Interactions in the Solid State

Adonin, Sergey A.; Novikov, Alexander S.; Sokolov, Maxim N.

doi:10.1002/ejic.201900349

Cited by 10 publications

(4 citation statements)

References 49 publications

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“…The QTAIM analysis demonstrates the presence of appropriate bond critical points (BCPs) for various intermolecular noncovalent interactions in 1 – 3 (Table ). The low magnitude of the electron density (0.002–0.019 au), positive values of the Laplacian of electron density (0.006–0.058 au), and very close to 0 positive energy density (0.001–0.002 au) in these BCPs are typical for noncovalent interactions involving halogen − and gold atoms. , For bifurcated XBs, in addition to the two BCPs that correspond to the halogen–halogen contacts, the ring critical points were observed in the characteristic triangular regions formed by the bond paths. We defined the energies for all studied contacts according to the procedures proposed by Espinosa et al, Vener et al, and Tsirelson et al (the latter approach was developed exclusively for noncovalent contacts involving halogen atoms), and the estimated strength for each individual contact does not exceed 4.1 kcal/mol.…”

Section: Resultsmentioning

confidence: 89%

Bifurcated Halogen Bonding Involving Diaryliodonium Cations as Iodine(III)-Based Double-σ-Hole Donors

Aliyarova

Ivanov

Soldatova

et al. 2021

Crystal Growth & Design

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Three diaryliodonium tetrachloroaurates(III), [Ar1IAr2][AuCl4] (Ar1/Ar2 = Ph/Ph (1), Ph/Mes (2), o-(C6H4)2 (3)), were obtained as solids (62–80%) by the metathetical reaction of [Ar1IAr2](CF3CO2) and H[AuCl4]. In particular, the single-crystal X-ray diffraction studies of 1–3 revealed three-center bifurcated C–I···(Cl–Au–Cl) halogen bond (XB) and the more conventional interionic two-center C–I···Cl–Au XB. An XB with the iodine(III) center of a diaryliodonium cation can be formed even when ∠(C–I···X) is much less than 180° (decrease by 55° in our experiments). A Cambridge Structural Database search and processing revealed other examples of bifurcated XBs involving diaryliodonium species. All recognized bifurcated XBs with diaryliodonium cations were classified and divided into two categories: “bifurcated plus two-center” and “double-bifurcated” structural types. The nature and energies of the XB interactions were studied by density functional theory (DFT) calculations and a topological analysis of the electron density distribution in the framework of the quantum theory of atoms in molecules (QTAIM) at the ωB97XD/DZP-DKH level of theory. The nature of all XB contacts is purely noncovalent, and the total energy of bifurcated XBs is generally ca. 50% higher than the energy of two-center XBs.

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Section: Resultsmentioning

confidence: 89%

Bifurcated Halogen Bonding Involving Diaryliodonium Cations as Iodine(III)-Based Double-σ-Hole Donors

Aliyarova

Ivanov

Soldatova

et al. 2021

Crystal Growth & Design

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“…The low magnitude of the electron density (0.007–0.016 au), positive values of the Laplacian of electron density (0.023–0.058 au), and very close to zero positive energy density (0.001–0.002 au) in these bond critical points (3, −1) and estimated strength for appropriate short contacts (viz. 0.9 kcal·mol –1 for intermolecular Au···Cl contacts, 2.2 and 3.8 kcal·mol –1 for intermolecular Au···Cl contacts) are typical for such noncovalent interactions involving metal centers and halogen atoms in similar chemical systems. − …”

Section: Resultsmentioning

confidence: 99%

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Shmelev

Okubazghi

Abramov

et al. 2022

Crystal Growth & Design

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A series of new cationic complexes [(PPh3)Au(L)](OTf) (L = 1,10-phenanthroline (phen) (1); 5,6-dimethyl-1,10-phenanthroline (dmphen) (2); 5,6-epoxy-5,6-dihydro-1,10-phenanthroline (ephen) (3); dimethyl 2,2’-biquinoline-4,4’-dicarboxylate (dmcbiq) (4); 2,3,4,5,6,7,8,9-octachloro-1,10-phenantroline (ocphen) (5)) were obtained in high yields by the standard ligand exchange reactions from [(PPh3)AuCl]. The compounds were characterized by analytical and spectroscopic methods. For all compounds, the crystal structure was established using X-ray diffraction analysis. In all structures, an atypical asymmetric mode of coordination of the diimine ligand (one shortened and the second elongated Au–N bond) was found, which is a consequence of the so-called antichelate effect. Structures 1–3 with electron-donating substituents (H, methyl, epoxide) are the most asymmetric, while structures 4 and 5 with electron-withdrawing groups (CO2Me and Cl) are the least asymmetric. According to the results of the density functional theory (DFT) calculations, both Au–N bonds are covalent, and the geometry around gold(I) can be considered as a distorted triangular one. Cationic complexes [(PPh3)Au(L)]+ form dimers in the crystal structure due to π–π interactions, the calculated energy of which reaches 4.2 kcal·mol–1 in the case of structure 5. These dimers in 5 additionally interact with OTf– anions through different kinds of contacts with a calculated total energy of 8.8 kcal·mol–1. Inside the {[(PPh3)Au(ocphen)]2}2+ associates, intermolecular Au···Cl noncovalent interactions were also found. Remarkably, the dimers in 5 are built through nonclassical π–π interactions between geometrically different parts of the ocphen ligand, which is a consequence of its asymmetric coordination to the gold(I) center. All complexes show multiple photoluminescence in the solid state at room temperature. The lifetimes of the excited state are in the microsecond range, which is characteristic of phosphorescence. Time-dependent DFT (TD-DFT) calculations reveal that electronic transitions of different nature are responsible for the photoluminescence of complexes 1–5.

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“…The metal/ligand stoichiometry, as well as the temperature and concentration, along with the kind of counter ion utilized throughout the reaction process, can all affect how the coordination polymers are made. Additionally, the coordination geometry of the various metal ions used to create these CPs has attracted a lot of study [ 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 ].…”

Section: Introductionmentioning

confidence: 99%

Progress in the Field of Cyclophosphazenes: Preparation, Properties, and Applications

Dagdag,

Kim

2023

Polymers

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This review article provides a comprehensive overview of recent advancements in the realm of cyclophosphazenes, encompassing their preparation methodologies, distinctive properties, and diverse applications. The synthesis approaches are explored, highlighting advancements in the preparation of these cyclic compounds. The discussion extends to the distinctive properties exhibited by cyclophosphazenes, including thermal stability characteristics, and other relevant features. Furthermore, we examine the broad spectrum of applications for cyclophosphazenes in various fields, such as coatings, adhesives, composites, extractants, metal complexes, organometallic chemistry, medicine, and inorganic chemistry. This review aims to offer insights into the evolving landscape of cyclophosphazenes and their ever-expanding roles in contemporary scientific and technological arenas. Future possibilities are emphasized, and significant research data shortages are identified.

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Polymeric Lead(II) Iodoacetate: Pb···I and I···I Non‐Covalent Interactions in the Solid State

Cited by 10 publications

References 49 publications

Bifurcated Halogen Bonding Involving Diaryliodonium Cations as Iodine(III)-Based Double-σ-Hole Donors

Bifurcated Halogen Bonding Involving Diaryliodonium Cations as Iodine(III)-Based Double-σ-Hole Donors

Asymmetric Coordination Mode of Phenanthroline-like Ligands in Gold(I) Complexes: A Case of the Antichelate Effect

Progress in the Field of Cyclophosphazenes: Preparation, Properties, and Applications

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