B–H<sub>b</sub>⋯π interaction in borane–graphene complexes: coronene as a case study

Saha, Bapan; Bhattacharyya, Pradip

doi:10.1039/c7nj00057j

Cited by 17 publications

(79 citation statements)

References 89 publications

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“…Boron‐hydrogen compounds are receiving a lot of attention due to their diverse physical and chemical properties, which can be useful for various technological applications ranging from hydrogen storage, fuel cells to high conducting materials even at room temperature as well as for applications in medicinal chemistry . Boranes and carboranes are recently targeted because of their potential to form

BH \cdot \cdot \cdot π

interactions with the π ‐face of an arene . It has been suggested that these

BH \cdot \cdot \cdot π

interactions may be driven by a nonspecific weak dispersion contact, as for example based on restrained fit to the electrostatic potential and symmetry‐adapted perturbation theory studies or molecular orbital analyses .…”

Section: Introductionmentioning

confidence: 99%

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

et al. 2019

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We report the thermodynamic stabilities and the intrinsic strengths of three‐center‐two‐electron B−B−B and B−Hb−B bonds (Hb : bridging hydrogen), and two‐center‐two‐electron B−Ht bonds (Ht : terminal hydrogen) which can be served as a new, effective tool to determine the decisive role of the intermediates of hydrogenation/dehydrogenation reactions of borohydride. The calculated heats of formation were obtained with the G4 composite method and the intrinsic strengths of B−B−B, B−Hb−B, and B−Ht bonds were derived from local stretching force constants obtained at the B3LYP‐D2/cc‐pVTZ level of theory for 21 boron‐hydrogen compounds, including 19 intermediates. The Quantum Theory of Atoms in Molecules (QTAIM) was used to deepen the inside into the nature of B−B−B, B−Hb−B, and B−Ht bonds. We found that all of the experimentally identified intermediates hindering the reversibility of the decomposition reactions are thermodynamically stable and possess strong B−B−B, B−Hb−B, and B−Ht bonds. This proves that thermodynamic data and intrinsic B−B−B, B−Hb−B, and B−Ht bond strengths form a new, effective tool to characterize new (potential) intermediates and to predict their role for the reversibility of the hydrogenation/dehydrogenation reactions.

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BH \cdot \cdot \cdot π

interactions with the π ‐face of an arene . It has been suggested that these

BH \cdot \cdot \cdot π

Section: Introductionmentioning

confidence: 99%

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

et al. 2019

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“…Molecular electrostatic potential (MEP) surface describes the distribution of charge density around the atom or groups of molecular systems and it provides crucial information about the reactivity of a particular site . Apart from this, these surfaces are also widely used to predict the feasibility of interaction between two moieties ,. Therefore, the MEP surfaces of the considered un‐doped and doped tetracene, chrysene and triphenylene are obtained, Figure .…”

Section: Resultsmentioning

confidence: 99%

“…The observed results can be attributed to the existence of moderately weak interaction with solvent media. Generally for weaker interactions, the effect of solvent dielectric is less pronounced as compared to the stronger interaction ,…”

Section: Resultsmentioning

confidence: 99%

“…Apart from this, reports are also there which in favour of electrostatic interaction . Furthermore, extent of contribution from these interactions varies with the nature of the systems (presence of substituent, dopants etc) and thus becomes important to have some understanding about it . Use of appropriate DFT functional in this regard is handy.…”

Section: Resultsmentioning

confidence: 99%

“…Presence of heteroatoms in their aromatic frameworks leads to charge separation on the surface of the PACs and modulate their electronic and molecular properties. Moreover, the modulated charge separation due to presence of heteroatoms in the rings also promotes variety of interactions ,. In the midst of these, π⋯π stacking or aromatic stacking plays a key role in influencing the reactivity, stability of many processes such as molecular recognition, stabilizing host‐guest systems, DNA and protein structures etc ,.…”

Section: Introductionmentioning

confidence: 99%

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DFT Study on the Formation of Homo and Hetero dimers of BN‐doped Tetracyclic fused Aromatics via π⋯π Stacking

Saha¹,

Bhattacharyya

2019

ChemistrySelect

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Computational study on the formation of 31 homo and hetero dimers of tetracyclic fused aromatics (isomeric) viz. tetracene, chrysene and triphenylene via π⋯π stacking is performed using Density functional theory (DFT). Geometries of the BN doped tetracene, chrysene and triphenylene and their complexes are studied. Stability of the complexes, measured in terms of stabilization energies (SEs) advocate in favour of stability of the complexes in both gas and solvent phases (10.37‐19.09 kcal mol‐1). Effect of BN doping on the stability of the complexes is also scrutinized with respect to its position and number. Studies also confirmed the prominent role of dispersive interaction in stabilizing the complexes. Thermochemical analysis reveals the exothermic nature and spontaneity of the complexation process. TD‐DFT (time dependent density functional theory) study showed significant red shift in the absorption spectra upon complexation.

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B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

Saha

Bhattacharyya

2018

Int J of Quantum Chemistry

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Density functional theory calculation on BAH b :X interaction (X5 N, O, P, S, F, Cl, Br) is performed. HOMO energy predicts the feasibility of such complexation. Steric and electronic effects play significant role on geometry of the complexes. Interaction energy suggests that the interaction is moderately strong (< 5.00 kcal mol 21 ) in nature and the complexes are stable in both gas and solvent phase. Electron donating group on: X facilitates the interaction whereas electron withdrawing group impedes the same. MP2 and CCSD(T) calculations further confirm the suitability of xB97X-D and M06-2X functional for studying such interactions. Dispersive interaction is the primary mode of interaction in stabilizing the complexes. 1 H NMR and IR study are also performed.Thermochemical analysis advocates exothermic nature of complexation.B2H b :X interaction, CCSD(T), DFT, MP2, stabilization energy, thermochemical analysis 1 | I N TR ODU C TI ON Noncovalent interactions such as hydrogen bonding, stacking, dispersion interaction, hydrophobic interaction, interaction with p systems (anionÁÁÁp, CAHÁÁÁp, OAHÁÁÁp, NAHÁÁÁp, SAHÁÁÁp, cationÁÁÁp) and halogen bonding have drawn attention owing to their potential application in different fields [1][2][3][4] and play significant role in controlling different physical, chemical, and biological phenomena in crystal engineering, drug designing, protein folding, molecular recognition process, and supramolecular chemistry. [2,[5][6][7][8][9][10][11][12][13][14] These interactions are classified depending on their origin, nature, and strength. [8] Hydrogen bonding is one of the most versatile and extensively studied noncovalent interaction [15][16][17] that plays an essential role in the function, dynamics, and structure of biological and chemical systems. Hydrogen bonding interactions can be either conventional or nonconventional. [18] In conventional hydrogen bonding, DAHÁÁÁA, both D (donor) and A (acceptor) atoms are highly electronegative (usually N, O, F) whereas in nonconventional case D and A may both be less electronegative.A relatively new and less known nonconventional interaction is the BAHÁÁÁp interaction in which both terminal (H t ) and bridging (H b ) hydrogens of boranes interact with interaction in which both terminal (H t ) and bridging (H b ) hydrogens of boranes interact with electron rich p systems. [19,20] However, partially negative H t (H d-) of borane is reluctant to form stable BAH t ÁÁÁp interactions. In contrast, H b is partially positive (H d1 ) due to its involvement in the formation of two electron-three center (2eA3c) bond and thereby results a stable BAH b ÁÁÁp interaction. [20] Recently, new type of noncovalent interaction involving lone pairs (nonbonded pairs) has also been explored. [8] Lone pair of electrons not only control the geometry but also play a decisive role in the chemistry of the species. Amongst the interactions involving lone pair, lone pairÁÁÁp interaction is widely studied [4,18] and was first identified in the structure of Z-DNA. [21] How...

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B–H_b⋯π interaction in borane–graphene complexes: coronene as a case study

Abstract: N/B/BN doping in graphene enhances adsorption of boranes.

Cited by 17 publications

References 89 publications

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

DFT Study on the Formation of Homo and Hetero dimers of BN‐doped Tetracyclic fused Aromatics via π⋯π Stacking

B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

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B–Hb⋯π interaction in borane–graphene complexes: coronene as a case study

Abstract: N/B/BN doping in graphene enhances adsorption of boranes.

Cited by 17 publications

References 89 publications

Quantitative Assessment of B−B−B, B−Hb−B, and B−Ht Bonds: From BH3 to B12H122−

Quantitative Assessment of B−B−B, B−Hb−B, and B−Ht Bonds: From BH3 to B12H122−

DFT Study on the Formation of Homo and Hetero dimers of BN‐doped Tetracyclic fused Aromatics via π⋯π Stacking

B−Hb←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

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B–H_b⋯π interaction in borane–graphene complexes: coronene as a case study

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study