Macrocycle Embrace: Encapsulation of Fluoroarenes by <i>m</i>‐Phenylene Ethynylene Host

Popov, Ilya; Chen, Teng‐Hao; Belyakov, Sergey; Daugulis, Olafs; Wheeler, Steven E.; Miljanić, Ognjen Š.

doi:10.1002/chem.201406073

Cited by 26 publications

(22 citation statements)

References 84 publications

(17 reference statements)

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“…However, for the IVM molecule, the electrostatic potential obtained from the DFT calculation of the distribution of electron density does not contain significant extrema. This is also the case for other macrocyclic molecules [40]. For this reason, molecules of IVM can form inclusion compounds with polar molecules due to the formation of hydrogen bonds.…”

Section: Molecular Structure In the Crystal Cellmentioning

confidence: 79%

Crystal Structures of New Ivermectin Pseudopolymorphs

2021

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New pseudopolymorphs of ivermectin (IVM), a potential anti-COVID-19 drug, were prepared. The crystal structure for three pseudopolymorphic crystalline forms of IVM has been determined using single-crystal X-ray crystallographic analysis. The molecular conformation of IVM in crystals has been compared with the conformation of isolated molecules modeled by DFT calculations. In a solvent with relatively small molecules (ethanol), IVM forms monoclinic crystal structure (space group I2), which contains two types of voids. When crystallized from solvents with larger molecules, like -valerolactone (GVL) and methyl tert-butyl ether (MTBE), IVM forms orthorhombic crystal structure (space group P212121). Calculations of the lattice energy indicate that interactions between IVM and solvents play a minor role; the main contribution to energy is made by the interactions between the molecules of IVM itself, which form a framework in the crystal structure. Interactions between IVM and molecules of solvents were evaluated using Hirshfeld surface analysis. Thermal analysis of the new pseudopolymorphs of IVM was performed by differential scanning calorimetry and thermogravimetric analysis.

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Section: Molecular Structure In the Crystal Cellmentioning

confidence: 79%

Crystal Structures of New Ivermectin Pseudopolymorphs

2021

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“…Similar [π⋅⋅⋅π] stacking, wherein two molecules of 1 form a unique complex building block, is also observed in the structure of Zr‐MCMOF; this stacking distorts the Zr 6 secondary building unit (SBU) in Zr‐MCMOF, generating a layered structure rare among Zr‐based MOFs . In our previous work, an ester derivative of macrocycle 1 was shown to encapsulate fluoroarenes inside its cavity; thus, the 1D channels in Zr‐MCMOF appear to be a unique microenvironment, promising for applications in highly specific separations.…”

Section: Figurementioning

confidence: 99%

A Zirconium Macrocyclic Metal–Organic Framework with Predesigned Shape‐Persistent Apertures

Chen

Popov

Miljanić

2016

Chemistry A European J

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A microporous metal-organic framework (MOF) was synthesized from [Zr O (OH) (C H COO) ] clusters and a triacid ligand based on a shape-persistent arylene ethynylene macrocycle. This framework, dubbed Zr-MCMOF, is held together by metal-ligand coordination and multiple weak interactions: hydrogen bonding, [π⋅⋅⋅π] stacking, and [C-H⋅⋅⋅π] interactions. The rigid ligand has a 9 Å-wide central void, which serves as a predesigned aperture for the 1D channels; all of the porosity of Zr-MCMOF comes from the ligand. The resulting framework possesses high hydrolytic and thermal stability and a flexible structure unique among Zr-based MOFs.

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“…[6] Among the numerousS PMs, arylene ethynylenem acrocycles( AEMs) are the most widely studied and many interesting applications based on AEMs have emerged. [7][8][9][10][11][12][13][14] Recent advances in dynamic covalent chemistry, [15][16][17] namely alkyne metathesis, have enabled the facile access to AEMs on gram scale, and boosted the applicationso ft hese macrocycles towardm aterials development. [18][19][20] It has been reported that the self-association of AEMs is induced by face-to-face p-p interactions between aromatic rings and is strongly influenced by the rigidity of the backbone structuresa nd pendant functional groups of the macrocycles: Electron-withdrawings ubstituents promotes elf-aggregation of macrocycles, whereas electron-donating functional groups have the opposite effect;ap lanar and rigid framework enhances the aggregation, whereas aflexible nonplanar geometry inhibits it.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Phenylene Vinylene Macrocycles through Acyclic Diene Metathesis Macrocyclization and Their Aggregation Behavior

Zhang

Long

et al. 2015

Chemistry A European J

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A series of phenylene vinylene macrocycles (PVMs) bearing substituents with various sizes and electronic properties have been synthesized through a one-step acyclic diene metathesis macrocyclization approach and their aggregation behaviors have been investigated. In great contrast to the aggregation of the analogous phenylene ethynylene macrocycles, which aggregate only when substituted with electron-withdrawing groups, these PVMs undergo exceptionally strong aggregation, regardless of the electron-donating or -withdrawing characters of the substituents. The unusual aggregation behavior of the PVMs is further investigated with thermodynamic and computer modeling studies, which show a good agreement with the recently proposed direct through-space interaction model, rather than the polar/π model. The high aggregation tendency of PVMs suggests the great potential of this novel class of shape-persistent macrocycles in a variety of applications, such as ion channels, host-guest recognition, and catalysis.

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Macrocycle Embrace: Encapsulation of Fluoroarenes by m‐Phenylene Ethynylene Host

Cited by 26 publications

References 84 publications

Crystal Structures of New Ivermectin Pseudopolymorphs

Crystal Structures of New Ivermectin Pseudopolymorphs

A Zirconium Macrocyclic Metal–Organic Framework with Predesigned Shape‐Persistent Apertures

Synthesis of Phenylene Vinylene Macrocycles through Acyclic Diene Metathesis Macrocyclization and Their Aggregation Behavior

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