Deciphering Noncovalent Interactions Accompanying 7,7,8,8‐Tetracyanoquinodimethane Encapsulation within Biphene[<i>n</i>]arenes: Nucleus‐Independent Chemical Shifts Approach

Lande, Dipali N.; Rao, Soniya S.; Gejji, Shridhar P.

doi:10.1002/cphc.201600186

Cited by 27 publications

(14 citation statements)

References 70 publications

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“…The present work analyzes calix[4]tetrolarene conformers and their derivatives. The density functional theory (DFT) incorporating the global hybrid meta GGA (M06-2X) functional, which simulates well the hydrogen bonding and adequately typifies other weak interactions, has been applied in conjunction with the internally stored 6-311++G(d,p) basis set (the polarized and diffuse functions being added to all atoms). − Stationary point structures exhibiting qualitatively different hydrogen-bonded patterns were optimized using the Gaussian 09 suite of programs . Normal vibrational frequencies in various conformers were computed for the stationary point structures, which were confirmed to be the local minima on multidimensional potential energy surfaces.…”

Section: Computational Strategymentioning

confidence: 99%

Exploring Chimeric Calix[4]tetrolarene Molecular Scaffolds: Theoretical Investigations

Lande

Gejji

2018

J. Phys. Chem. A

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The structure and spectral characteristics of the chimeric mixture of calixarene and pyrogallolarene (usually referred to as calix[4]tetrolarene) and its derivatives are studied employing the M06-2X-based density functional theory. Different conformers, viz., cone, partial cone, 1,2-alternate, and 1,3-alternate, were identified as the stationary point structures on their potential energy surfaces. Among these, the symmetric C cone conformer is found to be energetically favorable, which can be attributed to the cyclic array of hydrogen-bonding network in the calix[4]tetrolarene or its thia analogue. The substitution of methoxy groups at the upper rims of calix[4]tetrol- and thicalix[4]tetrol-arenes significantly influences the cooperative hydrogen-bonding network and conformational behavior of these hosts. The methoxy-substituted macrocycles show lowering in symmetry from C to C, engendering the pinched cone conformer to be the lowest energy structure. The enhanced solubility of the modified calix[4]tetrolarene macrocycles has been further explained from diminutive cooperative hydrogen bonding in its top rim compared to the pyrogallolarene, which is evidenced from the quantum theory of atoms in molecule and noncovalent interaction reduce density gradient method. Discernibly, the underlying cooperative hydrogen bonding emerges its signature in the characteristic vibrational patterns of the calixarene-based molecular scaffolds. The chemical shift parameters in their H NMR spectra have further been characterized.

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Section: Computational Strategymentioning

confidence: 99%

Exploring Chimeric Calix[4]tetrolarene Molecular Scaffolds: Theoretical Investigations

Lande

Gejji

2018

J. Phys. Chem. A

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“…The vibrational and 1 H NMR spectra of individual hosts, guests and their complexes which serve as fingerprint for typifying molecular interactions in host guest chemistry are presented. The computational method used can be found in the Supporting Information.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Binding of bis‐naphthalene Cleft based Molecular Tubes

Lande¹,

Gejji²

2018

ChemistrySelect

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The endo‐functionalized bis‐urea molecular tubes having the rigid bis‐naphthalene cleft aligned parallel or antiparallel to each other yield syn (SBU) and anti (ABU) configurational isomers which exhibit remarkable selectivity toward guest binding. In the present work the noncovalent binding from SBU and ABU receptors with heterocyclic guests viz., pyridine (py) and pyrazine (pz) is unveiled through the density functional theory. The complexation is spontaneous, thermodynamically favorable and facilitated via N−H⋅⋅⋅N hydrogen bonding, C−H⋅⋅⋅π and other non‐covalent interactions. The coexistence of multiple intermolecular interactions reflects in the infrared and 1H NMR spectra. The ‘frequency shift’ of the characteristic vibrations accompanying the complexation is rationalized. Encapsulation of py or pz within π‐electron rich cavity of the ABU led to shielding of the guest protons while hydrogen bonded protons engender downfield signals in the calculated 1H NMR spectra.

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“…[6] Owing to their intrinsic characteristics and properties such as easy accessibility,c onvenient functionalization, unique topological structures, and nice inclusion properties, biphen[n]arenes could be the next popular scaffold in supramolecular chemistry. [6][7][8][9][10] Huang, [7a] Yu, [7b] and our group [7c] prepared water-soluble biphen [3]arenes and demonstrated their recognition/assembly behavior in water solution.Y ue tal. [8] reported the synthesis and host-guest complexation of ah ybrid[3]arene bearing two 1,3,5-trimethoxybenzeneu nits and one biphenarene monomer unit (4,4'-biphenold iethyle ther).…”

Section: Introductionmentioning

confidence: 99%

“…Owing to their intrinsic characteristics and properties such as easy accessibility, convenient functionalization, unique topological structures, and nice inclusion properties, biphen[ n ]arenes could be the next popular scaffold in supramolecular chemistry . Huang, Yu, and our group prepared water‐soluble biphen[3]arenes and demonstrated their recognition/assembly behavior in water solution.…”

Section: Introductionmentioning

confidence: 99%

“…reported the synthesis and host–guest complexation of a hybrid[3]arene bearing two 1,3,5‐trimethoxybenzene units and one biphenarene monomer unit (4,4′‐biphenol diethyl ether). By using DFT calculations, the group of Gejji investigated the driving forces for the encapsulation of 7,7,8,8‐tetracyanoquinodimethane (TCNQ) within ethylated biphen[4]arene.…”

Section: Introductionmentioning

confidence: 99%

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Molecular Recognition Properties of Biphen[4]arene

Chen

et al. 2016

Chemistry An Asian Journal

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Biphen[n]arenes (n=3, 4) are a new family of macrocyclic hosts. Here, we describe the molecular recognition behavior of hydroxylated biphen[4]arene (OHBP4) for the first time. A series of cationic guests with different sizes and shapes, including quaternary ammonium salts (1⋅PF and 2⋅PF ), pyridinium-based guests (3⋅2 PF -6⋅2 PF ), and cobaltocenium hexafluorophosphate (7⋅PF ), were chosen as model guest molecules. OHBP4 exhibits good selectivity towards the 2,7-dibutyldiazapyrenium bis(hexafluorophosphate) (4⋅2 PF ) axle to form a [2]pseudorotaxane-type complex. In contrast, hydroxylated biphen[3]arene (OHBP3) cannot bind with this big guest. In addition, OHBP4 strongly interacts with adamantane derivative 2⋅PF and cobaltocenium 7⋅PF , which have tridimensional shape and relatively large size. The association constant of the 7 ⊂OHBP4 complex in 1:1 (v/v) [D ]acetone/CD Cl solution is up to 3100±300 m .

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Deciphering Noncovalent Interactions Accompanying 7,7,8,8‐Tetracyanoquinodimethane Encapsulation within Biphene[n]arenes: Nucleus‐Independent Chemical Shifts Approach

Cited by 27 publications

References 70 publications

Exploring Chimeric Calix[4]tetrolarene Molecular Scaffolds: Theoretical Investigations

Exploring Chimeric Calix[4]tetrolarene Molecular Scaffolds: Theoretical Investigations

Supramolecular Binding of bis‐naphthalene Cleft based Molecular Tubes

Molecular Recognition Properties of Biphen[4]arene

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