Understanding Trends in Molecular Bond Angles

Linker, G.; Duijnen, Piet Th. van; Broer, Ria

doi:10.1021/acs.jpca.9b10248

Cited by 14 publications

(8 citation statements)

References 54 publications

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“…Such an orientation of the surfactant molecules (Figure c) leaves the vibrational bands of the hydrocarbon chain due to different alkyl groups largely unaffected, while that of (CH 2 ) wagg at 1341–1360 cm –1 completely disappears. It happens due to a change in the angle of atoms of the methylene group versus the plane of the SDS molecule in the event of compact bilayer formation among the hydrocarbon chains. , Since the interactions are happening through oppositely charged head groups of SDS and 16- n -16, the frequency of the doublet of SDS (SO 2 ) depends on the spacer length of 16- n -16 (Figure b), which even merges into a single peak for 16-2-16 as well as 16-3-16, indicating much stronger adsorption due to a better compatibility between the SDS layer and the spacer length of two to three methylene groups of 16- n -16. The effect is minimum for CTAB, supplementing our earlier conclusion that surface adsorption of 16- n -16 is much stronger than that of CTAB.…”

Section: Resultsmentioning

confidence: 99%

Ag and Au Nanoparticles as Color Indicators for Monomer/Micelle–Nanoparticle Interactions

et al. 2022

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Ag and Au nanoparticles (NPs) were used as color indicators to determine the monomer/micelle adsorption on the NP surface. A simple methodology based on the color change of Ag/Au NPs upon interacting with surface-active molecules was developed. A contrasting color change occurred when NPs interact with the monomer/micelle. This was demonstrated by monitoring the adsorption behavior of a series of Gemini surfactants. UV–visible measurements showed a large change in the intensity and wavelength of Ag/Au NP absorbance upon the surface adsorption of the monomer/micelle of Gemini surfactants. The mechanism of surface adsorption and molecular orientation on the solid–liquid interface of NPs was determined by performing the FT-IR and XPS measurements. Results demonstrated that sharp color changes from yellow to red for Ag NPs and red to purple for Au NPs happened when the Gemini surfactant monomer/micelle adsorbs on the NP surface. This colorimeter-based methodology highlighted the applicability of Ag/Au NPs in complex media where such NPs frequently encounter surface-active molecules.

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Section: Resultsmentioning

confidence: 99%

Ag and Au Nanoparticles as Color Indicators for Monomer/Micelle–Nanoparticle Interactions

et al. 2022

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“…The Si−X−Al bond angle decreases abruptly from 121.5° to 93.0° as the interacting halogen atom in Si−X−Al becomes increasingly heavier from F to Cl to Br (Set 4). Decreasing trend of bond angle can be attributed to the increasing polarizability of the halogens from F to Br [65] …”

Section: Resultsmentioning

confidence: 99%

“…Decreasing trend of bond angle can be attributed to the increasing polarizability of the halogens from F to Br. [65] The SiÀ X bond of the halosilane gets elongated upon complexation with the acceptor. Elongation of the SiÀ X bond ranges from 0.009 Å in SiH 3 FÀ BBr 3 to 0.099 Å in SiH 3 FÀ Al(CF 3 ) 3 .…”

Section: Chemistryselectmentioning

confidence: 99%

Halide‐Triel Bonds between R₃SiX (X=F, Cl and Br) and TrY₃ (Tr=Al, B and Ga)

Deuri¹,

Pathak²

2023

ChemistrySelect

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Halide‐triel bonds between halosilane donors and alane/borane/gallane acceptors are investigated considering 24 model complexes using quantum chemical calculations. Nature and strength of Si−X….Tr interactions (X=F, Cl, Br and Tr=Al, B, Ga) binding these complexes has been studied using Electrostatic Potential (ESP), Quantum Theory of Atoms in Molecules (QTAIM), Natural Bond Orbital (NBO), and Energy Decomposition Analysis (EDA) techniques. Basis Set Superposition Error (BSSE) corrected binding energy of the complexes ranges from −3.19 to −29.40 kcal mol−1. QTAIM parameters Laplacian and the total electron density at the Bond Critical Points (BCPs) indicate that the halide‐triel bonds studied here are largely electrostatic in nature (closed‐shell interactions); this has also been revealed through ESP analysis and EDA scheme. In addition, role of charge transfer in these halide‐triel bonds has also been established through NBO analysis. Two charge transfer orbital interactions are responsible for the primary interaction Si−X….Tr: n(F/Cl/Br)→n*(Al/Ga/B)4pt ${n(F/Cl/Br)\to {n}^{^{\ast}}(Al/Ga/B){\rm \ }}$ and σ(Si−X) →4ptn*(Al/Ga) ${\to {\rm \ }{n}^{^{\ast}}(Al/Ga)}$ . EDA analysis identifies electrostatic term as the biggest contributor towards the binding of the complexes followed by the polarisation and dispersion terms in most of the complexes. Results of this study have relevance in the Si−F bond activation methodology in organic synthesis.

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“…It clearly shows that the electron density of the C–Cl bond is slightly higher than that of C–F and C–Br for halogen-substituted cycloheptane, thus confirming a strong covalent interaction between the halogens and the ring as indicated by the color code in the RDG plot. However, the sign of the second eigenvalue of the electron density (ED) Hessian matrix, which clearly distinguishes repulsive (λ 2 > 0) interaction from attractive (λ 2 < 0) interactions shows that the sign(λ 2 )ρ for the molecules is >0, indicating the presence of slight repulsive interactions and strong covalent interactions − in the molecules as indicated by the intrinsic bond strength index scale. In the case of oxepane, azepane, and thiepane, the result shows that the C–N bond has a higher ED than C–O and C–S bonds, suggesting stronger covalent interactions.…”

Section: Results and Discussionmentioning

confidence: 99%

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

et al. 2022

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The application of plain cycloalkanes and heterocyclic derivatives in the synthesis of valuable natural products and pharmacologically active intermediates has increased tremendously in recent times with much attention being paid to the lower cycloalkane members. The structural and molecular properties of higher seven-membered and nonaromatic heterocyclic derivatives are less known despite their stable nature and vast application; thus, an insight into their structural and electronic properties is still needed. Appropriate quantum chemical calculations utilizing the ab initio (MP2) method, meta-hybrid (M06-2X) functional, and long-range-separated functionals (ωB97XD) have been utilized in this work to investigate the structural reactivity, stability, and behavior of substituents on cycloheptane (CHP) and its derivatives: azepane, oxepane, thiepane, fluorocycloheptane (FCHP), bromocycloheptane (BrCHP), and chlorocycloheptane (ClCHP). Molecular global reactivity descriptors such as Fukui function, frontier molecular orbitals (FMOs), and molecular electrostatic potential were computed and compared with lower members. The results of two population methods CHELPG and Atomic Dipole Corrected Hirshfeld Charges (ADCH) were equally compared to scrutinize the charge distribution in the molecules. The susceptibility of intramolecular interactions between the substituents and cycloalkane ring is revealed by natural bond orbital analysis and intramolecular weak interactions by the independent gradient model (IGM). Other properties such as atomic density of states, intrinsic bond strength index (IBSI), and dipole moments are considered. It is acclaimed that the strain effect is a major determinant effect in the energy balance of cyclic molecules; thus, the ring strain energies and validation of spectroscopic specificities with reference to the X-ray crystallographic data are also considered.

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Understanding Trends in Molecular Bond Angles

Cited by 14 publications

References 54 publications

Ag and Au Nanoparticles as Color Indicators for Monomer/Micelle–Nanoparticle Interactions

Ag and Au Nanoparticles as Color Indicators for Monomer/Micelle–Nanoparticle Interactions

Halide‐Triel Bonds between R₃SiX (X=F, Cl and Br) and TrY₃ (Tr=Al, B and Ga)

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

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Understanding Trends in Molecular Bond Angles

Cited by 14 publications

References 54 publications

Ag and Au Nanoparticles as Color Indicators for Monomer/Micelle–Nanoparticle Interactions

Ag and Au Nanoparticles as Color Indicators for Monomer/Micelle–Nanoparticle Interactions

Halide‐Triel Bonds between R3SiX (X=F, Cl and Br) and TrY3 (Tr=Al, B and Ga)

Meta-Hybrid Density Functional Theory Prediction of the Reactivity, Stability, and IGM of Azepane, Oxepane, Thiepane, and Halogenated Cycloheptane

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Halide‐Triel Bonds between R₃SiX (X=F, Cl and Br) and TrY₃ (Tr=Al, B and Ga)