The Quest for Large Group 13 Metallacalixarenes Based on Benzymidazolyl Ligands and Al and Ga Alkyls

Díaz-Ramírez, Mariana L.; Huggins, Hannah; Donnadieu, Bruno; López, Nazario; Muñoz‐Hernández, Miguel‐Ángel

doi:10.1002/ejic.202100583

Cited by 5 publications

(1 citation statement)

References 37 publications

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“…The dimensions, metal core, internal cavity, and functional units of metallocycles are the key factors for the further utilization of these supramolecular coordination complexes (SCCs) in the field of molecular recognition, catalysis, biomedicine, and chemical sensing . Among the many metal–organic macrocycles, bowl-shaped molecules, known as metallocavitands, synthesized from various naked/partially protected metal ions have attracted much research interest. − For instance, considerable attention has been devoted to the construction of fac -[Re(CO) 3 ] core-based metallocycles. − Over the past few years, neutral flexible bidentate donors consisting of diphenylmethane (−Ph–CH 2 –Ph−) or dimesitylenemethane as the central spacer and two terminal heterocycles, (benzimidazolyl/naphthanoimidazolyl/2-alkyl- or 2-phenyl-substituted benzimidazolyl), have been used in the self-assembly of dinuclear heteroleptic or mononuclear homoleptic metallocavitands. This assembly is achieved using a rigid bis-chelating donor, flexible bidentate ligands, and rhenium sources in the presence of high-boiling aromatic solvents via a one-pot solvothermal approach .…”

Section: Introductionmentioning

confidence: 99%

Solvent-Directed Rhenium(I) Metallocyclic Tubes, Dimeric Capsule, and Intercalated Dimers

Borkar,

Bhol,

Shankar

et al. 2024

Crystal Growth & Design

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Neutral flexible bidentate nitrogen donor ligands L n (L bim and L nim ) were designed, synthesized, and utilized as structural frameworks to construct solvent-directed rhenium(I) metallocyclic tubes, dimeric capsules, and intercalated dimers in the solid state. The combination of Re 2 (CO) 10 , 6,11-dihydroxy-5,12-naphthacenedione (H 2 -dhnq) or 1,4dihydroxyanthraquinone (H 2 -dhaq), and L bim or L nim in the presence of benzene (Bz), mesitylene (Mes), or p-xylene (p-xyl) resulted in neutral heteroleptic metallocyclic tubes fac-[{(CO) 3 Re(μ−dhnq)Re(CO) 3 }(μ− L bim )] (1), fac-[{(CO) 3 Re(μ−dhnq)Re(CO) 3 }(μ−L nim )] (2), or fac-[{(CO) 3 Re(μ−dhaq)Re(CO) 3 }(μ−L nim )] ( 3) with/without encapsulated guest solvent(s) depending on the nature of the solvent. Metallocyclic tubes 1 and 3 crystallized with solvent guest molecule(s) as (Bz) 2 @1, (Mes) 2 @1, (Bz)@3, and (p-xyl) 2 @3. On the other hand, metallocyclic tube 1 crystallized as a dimeric capsule (p-xyl)@1 2 in the presence of p-xylene, which acts as a glue between the two metallocyclic tubes stabilized via noncovalent interactions in the solid state. Metallocyclic tubes 2 and 3 in the presence of the mesitylene solvent crystallized as an intercalated dimeric assembly 2 2 •4(Mes) and 3 2 •4(Mes) in the solid state. The results reveal that along with the ligand motifs, the size and shape of methyl-and nonmethyl-substituted aromatic solvents influence the formation of the tubular architecture, dimeric capsule, or intercalated dimers. All of the compounds were confirmed by single-crystal X-ray diffraction analysis and characterized by various analytical and spectroscopic methods. The thermal stability of the assembled host−guest structures was studied by thermogravimetric analysis.

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Section: Introductionmentioning

confidence: 99%

Solvent-Directed Rhenium(I) Metallocyclic Tubes, Dimeric Capsule, and Intercalated Dimers

Borkar,

Bhol,

Shankar

et al. 2024

Crystal Growth & Design

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Tuning the Size and Geometry of Pd(II)-Based Metallacalixarenes by Varying the N-Containing Ligands: Synthesis, Structure, and Sensing Properties

Tong

Wen

Cui

et al. 2022

Crystal Growth & Design

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Four types of palladium(II)-based cup-shaped structures as structural analogues of [M3L3 ]3+-type metallacalix[3]arene, [M2L]2+-type semimetallacalix[4]arene, [M2L2 ]4+-type metallacalix[4]arene, and [M3L3 ]6+-type metallacalix[6]arene have been designed and synthesized via coordination-driven self-assembly using two types of imidazole- and dithiophene-containing ligands, [4,5-bis(2,5-dimethylthiophen-3-yl)-1H-imidazole (HL1 ) and bis(4,5-bis(2,5-dimethylthiophen-3-yl)-1H-imidazol-1-yl)methane (L2 )], with four types of palladium(II) nitrate precursors, (bpy)Pd(NO3)2 (M1 -NO3), (tmen)Pd(NO3)2 (M2 -NO3), (en)Pd(NO3)2 (M3 -NO3), and Pd(NO3)2 (M4 -NO3) (bpy = 2,2′-bipyridine; tmen = tetramethylethylenediamine; en = ethylenediamine). The difference in the imidazolate ligands and palladium(II) nitrate precursors in each complex brings about the variety of the structures and ion-encapsulating characteristics of the obtainable cavities in all the complexes. The fascinating multidimensional 2-D and 3-D highly ordered supramolecular configurations with metallacalixarenes as building blocks were constructed via π–π stacking and multiple hydrogen bonding. Furthermore, this successful strategy provides an insight into the construction of other more intricate structural analogues of metallacalixarenes and the chemistry in crystal engineering.

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Calix[4]arene-Analogous Technetium Supramolecules

et al. 2022

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Calix[4]arene-analogous technetium supramolecules (1 and 2) were assembled using (NBu4)[Tc2(μ-Cl)3(CO)6] and neutral flexible bidentate nitrogen-donor ligands (L1 and L2) consisting of four arene units covalently joined via methylene units. The neutral homoleptic technetium macrocycles adopt a partial cone/cone-shaped conformation in the solid state. These supramolecules are the first example of fac-[Tc(CO)3]+ core-based metallocalix[4]arenes and second example of fac-[Tc(CO)3]+ core-based metallomacrocycles. Structurally similar fac-[Re(CO)3]+ core-based macrocycles (3 and 4) were also prepared using [Re(CO)5X] (where X = Cl or Br) and L1 or L2. The products were characterized spectroscopically and by X-ray analysis.

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The Quest for Large Group 13 Metallacalixarenes Based on Benzymidazolyl Ligands and Al and Ga Alkyls

Cited by 5 publications

References 37 publications

Solvent-Directed Rhenium(I) Metallocyclic Tubes, Dimeric Capsule, and Intercalated Dimers

Solvent-Directed Rhenium(I) Metallocyclic Tubes, Dimeric Capsule, and Intercalated Dimers

Tuning the Size and Geometry of Pd(II)-Based Metallacalixarenes by Varying the N-Containing Ligands: Synthesis, Structure, and Sensing Properties

Calix[4]arene-Analogous Technetium Supramolecules

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