Behaviour of cation–pi interaction in presence of external electric field

Sarmah, Nabajit; Bhattacharyya, Pradip

doi:10.1039/c6ra21334k

Cited by 14 publications

(11 citation statements)

References 49 publications

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“…Our calculated distance of 1.826 Å is close to earlier reported value of 1.865 Å, as predicted by MP2/6‐311+G* level of theory . In addition, the benzene‐lithium cation dimer calculated complexation energy, with counterpoise corrected basis set superposition error (BSSE), is very high (−39.02 kcal/mol) and is close to the earlier reported CCSD(T)/6‐311+G(2d,2p) value of −37.11 kcal/mol and experimental estimate of −38.5 ± 3.2 kcal/mol …”

Section: Resultssupporting

confidence: 89%

“…[35,36,39,40,44,45] In addition, the benzenelithium cation dimer calculated complexation energy, with counterpoise corrected basis set superposition error (BSSE), is very high (−39.02 kcal/mol) and is close to the earlier reported CCSD(T)/6-311+G(2d,2p) value of −37.11 kcal/mol and experimental estimate of −38.5 ± 3.2 kcal/mol. [35][36][37]39,40,[42][43][44][45] Distance dependences of helium-3 chemical shift and its out-of-plane component for benzene are shown in Figure 5a and 5b. Both curves resemble the corresponding scans performed with Bq atom (see Figure 2).…”

Section: Benzene-and Pyrrole-3 He and LI + Scansmentioning

confidence: 99%

“…Finally, a lithium cation, used as a charge carrier in lithium batteries with graphite electrodes, could also be treated as an alternative magnetic probe of local aromaticity of ordered carbon systems . In addition, π– 7 Li + interactions are very important in molecular recognition, and 7 Li NMR spectroscopy is applied both in the solution and in the solid state …”

Section: Introductionmentioning

confidence: 99%

“…[34][35][36][37][38][39][40][41] In addition, π-7 Li + interactions are very important in molecular recognition, and 7 Li NMR spectroscopy is applied both in the solution and in the solid state. [35][36][37][38][39][40][41][42][43][44][45][46][47][48] In 2005, Stanger [1] proposed the so-called NICS-scan procedure as distance dependence criteria of aromaticity and antiaromaticity. By moving Bq probe from the origin of Cartesian coordinates (see Figure 1a and 1b) along zaxis up to 5 Å with step 0.1 Å, he calculated NICS(R) and NICS(R)zz profiles with respect to distance.…”

Section: Introductionmentioning

confidence: 99%

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Local aromaticity mapping in the vicinity of planar and nonplanar molecules

Kupka

Gajda

Stobiński

et al. 2019

Magnetic Reson in Chemistry

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We report on nucleus‐independent magnetic shielding (NICS) scans over the centers of six‐ and five‐membered rings in selected metal phthalocyanines (MPc) and fullerene C60 for more accurate characterization of local aromaticity in these compounds. Detailed tests were conducted on model aromatic molecules including benzene, pyrrole, indole, isoindole, and carbazole and subsequently applied to H2Pc, ZnPc, Al(OH)Pc, and CuPc. Similar behavior of three selected magnetic probes, Bq, 3He, and 7Li+, approaching perpendicularly the ring centers, was observed. For better visualization of shielding zone over the centers of aromatic rings, we introduced a simple mathematical procedure: the first and second derivatives of scan curves with respect to magnetic probe position enabled their additional examination. It allowed an easier localization of curve minimum and discrimination between areas in space varying by the magnetic field magnitude and to illustrate local aromaticity of two different kinds of rings in MPc with better resolution. Our results supported earlier reports on very low aromaticity indexes of pyrrole ring incorporated into MPc and significant aromaticity of the central macrocycle. No direct dependence between harmonic oscillator model of aromaticity and NICS was observed. Instead, a correlation between position of scan curve minimum and its magnitude were observed. In addition, the NICS values and 3He chemical shifts in the middle of neutral C60 and C606− anion agreed well with the reported experimental NMR values for He@C60 and He@C606−.

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Section: Resultssupporting

confidence: 89%

Section: Benzene-and Pyrrole-3 He and LI + Scansmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Local aromaticity mapping in the vicinity of planar and nonplanar molecules

Kupka

Gajda

Stobiński

et al. 2019

Magnetic Reson in Chemistry

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“…Both the strength and number of hydrogen bonds in water clusters can be tuned by EEFs, according to the theoretical investigation of Magrioties and coworkers [20d] . In addition, the response of bond strength to EEFs was addressed in noncovalent interactions with π orbitals, including π/π stacking, [20i,k] ion/π interactions, [20e–g] H‐ [20i,k] and X‐bonds [20l] . Notably, noncovalent interactions in EEFs were proposed as appropriate linkers for ‘smart materials’ [8–9,21b] .…”

Section: Introductionmentioning

confidence: 99%

Hydrogen and Halogen Bonding in Homogeneous External Electric Fields: Modulating the Bond Strengths

Chen

Dang

et al. 2021

Chemistry A European J

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Recent years have witnessed various fascinating phenomena arising from the interactions of noncovalent bonds with homogeneous external electric fields (EEFs). Here we performed a computational study to interpret the sensitivity of intrinsic bond strengths to EEFs in terms of steric effect and orbital interactions. The block-localized wavefunction (BLW) method, which combines the advantages of both ab initio valence bond (VB) theory and molecular orbital (MO) theory, and the subsequent energy decomposition (BLW-ED) approach were adopted. The sensitivity was monitored and analyzed using the induced energy term, which is the variation in each energy component along the EEF strength. Systems with single or multiple hydrogen (H) or halogen (X) bond(s) were also examined. It was found that the X-bond strength change to EEFs mainly stems from the covalency change, while generally the steric effect rules the response of H-bonds to EEFs. Furthermore, X-bonds are more sensitive to EEFs, with the key difference between H-and Xbonds lying in the charge transfer interaction. Since phenylboronic acid has been experimentally used as a smart linker in EEFs, switchable sensitivity was scrutinized with the example of the phenylboronic acid dimer, which exhibits two conformations with either antiparallel or parallel H-bonds, thereby, opposite or consistent responses to EEFs. Among the studied systems, the quadruple X-bonds in molecular capsules exhibit remarkable sensitivity, with its interaction energy increased by À 95.2 kJ mol À 1 at the EEF strength 0.005 a.u.

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